JPH0757737B2 - Polysiloxane-graft copolymer composition - Google Patents

Polysiloxane-graft copolymer composition

Info

Publication number
JPH0757737B2
JPH0757737B2 JP2207968A JP20796890A JPH0757737B2 JP H0757737 B2 JPH0757737 B2 JP H0757737B2 JP 2207968 A JP2207968 A JP 2207968A JP 20796890 A JP20796890 A JP 20796890A JP H0757737 B2 JPH0757737 B2 JP H0757737B2
Authority
JP
Japan
Prior art keywords
parts
monomers
composition
group
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2207968A
Other languages
Japanese (ja)
Other versions
JPH0376713A (en
Inventor
エドワード ガーベ ジェームス
シェパード カントナー スチーブン
クマー カンタ
ミトラ スマラジット
Original Assignee
ミネソタ マイニング アンド マニユフアクチユアリング カンパニー
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Publication date
Application filed by ミネソタ マイニング アンド マニユフアクチユアリング カンパニー filed Critical ミネソタ マイニング アンド マニユフアクチユアリング カンパニー
Publication of JPH0376713A publication Critical patent/JPH0376713A/en
Publication of JPH0757737B2 publication Critical patent/JPH0757737B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/22Esters containing halogen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/896Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/897Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing halogen, e.g. fluorosilicones
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/70Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7015Drug-containing film-forming compositions, e.g. spray-on
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair

Description

【発明の詳細な説明】 技術分野 本発明は、ペンダントシロキサンポリマー部分がグラフ
トされたビニルポリマー主鎖を有するコポリマーから成
る接着剤、表面改質用組成物、封止用組成物および局所
バインダーに関し、特に動物に対するようなかような被
覆の局所適用方法に関する。
TECHNICAL FIELD The present invention relates to adhesives, surface modifying compositions, sealing compositions and topical binders comprising copolymers having a vinyl polymer backbone grafted with pendant siloxane polymer moieties. In particular, it relates to a method of topical application of such a coating, such as for animals.

背景技術 感圧接着剤および接着剤被覆シートは、単なる接触だけ
で接着剤受容性表面に接着する能力を有するものとして
当業界において周知である。例えばラベルおよびテープ
形態のかような被覆シートは、非常に軽い「指圧」で各
種の基材に接着させ、かつ、後でそれが接着している表
面からシートを剥ぎ取ることによって除去できる。基材
に対する感圧接着剤(PSA)の初期親和性を減少させる
と同時に十分な最終接着力を維持させる(加圧接着後)
こともしばしば望ましいことである。先行技術では主と
してPSAと予め混合したまたはPSAの表面上に被覆した異
なる種類の「物理的スペーサー」を使用することによる
種々の方法でこの目的を達しようと試みている。かよう
なスペーサーは、所望の配置が得られるまで接着剤を基
材からわずかに遠ざけて保持する作用をする。例えば、
すべて本発明の譲受人に譲渡されたU.S.P.NOS.3,314,83
8、3,331,729および3,413,168には、ガラス、尿素−ま
たはフェノールホルムアルデヒド樹脂などから成る中
空、楕円形粒子を使用して初期接着力を減少させ、それ
によって位置調整性を得る方法が開示されている。マイ
クロバルーンは適用された手の圧力によって潰れまたは
破れ、その後にPSAが基材の表面に接触し、かつ、接着
することができると説明されている。しかし、潰れたま
たは破れたマイクロバルーンの断片は接着剤層に完全に
分散されないで接着剤の接着面上に残留し、これが少な
くとも初期に接着強さに不利な影響を与える。
Background Art Pressure sensitive adhesives and adhesive coated sheets are well known in the art as having the ability to adhere to an adhesive receptive surface with simple contact. Covering sheets such as those in the form of labels and tapes can be removed by adhering to various substrates with very light "acupressure" and later peeling the sheet from the surface to which it adheres. Reduces the initial affinity of the pressure sensitive adhesive (PSA) to the substrate while maintaining sufficient final adhesion (after pressure bonding)
It is also often desirable. The prior art attempts to reach this end in various ways, mainly by using different types of "physical spacers" premixed with PSA or coated on the surface of PSA. Such spacers act to hold the adhesive slightly away from the substrate until the desired placement is achieved. For example,
USPNOS.3,314,83, all assigned to the assignee of the present invention.
8,3,331,729 and 3,413,168 disclose methods of using hollow, elliptical particles, such as those made of glass, urea- or phenol-formaldehyde resins, to reduce the initial adhesion and thereby provide alignment. It is described that the microballoons are crushed or crushed by the applied hand pressure, after which the PSA can contact and adhere to the surface of the substrate. However, the collapsed or broken microballoon fragments are not completely dispersed in the adhesive layer and remain on the adhesive surface of the adhesive, which adversely affects the adhesive strength, at least initially.

シリコーンもPSA被覆の初期接着力を減少させ、それに
よって位置調整可能な製品を製造するためのスペーサー
物質として使用されてきた。例えば、U.S.P.NO.3,554,8
35(Morgan Adhesive Company)には、基材上でのラミ
ネートの位置調整が可能なように非接着性スペーサーと
してシリコーンの「点」(dots)または他の慣用の剥離
物質に依存する「滑り性」(slidable)PSA−被覆ラミ
ネートが開示されている。同様に、U.K.P.NO.1,541,311
(United Merchant and Manufacturers,Inc.)には、非
粘着性ポリシロキサンまたはポリシロキサン−ポリオキ
シアルキレンブロックコポリマーの小さいビーズまたは
小滴の形態の均一、かつ、不連続表面被覆によって位置
調整性が付与されているPSA−被覆ラミネートが記載さ
れている。両教示共に、シリコーンスペーサー物質を適
用し、次いで溶剤の除去、乾燥または硬化させるための
追加の製造工程が必要である。
Silicone has also been used as a spacer material to reduce the initial adhesion of PSA coatings, thereby producing alignable products. For example, USPNO.3,554,8
35 (Morgan Adhesive Company) relies on silicone "dots" or other conventional release materials as a non-adhesive spacer to allow alignment of the laminate on the substrate, or "slipperiness". (Slidable) PSA-coated laminates are disclosed. Similarly, UKP NO.1,541,311
(United Merchant and Manufacturers, Inc.) is provided with alignment properties by a uniform and discontinuous surface coating in the form of small beads or droplets of non-sticky polysiloxane or polysiloxane-polyoxyalkylene block copolymer. PSA-coated laminates are described. Both teachings require additional manufacturing steps to apply the silicone spacer material and then to remove, dry or cure the solvent.

U.S.P.NO.4,151,319(United Merchant and Manufactur
ers,Inc.)には、ポリシロキサンまたはポリシロキサン
−ポリオキシアルキレンブロックコポリマーの被覆をPS
A面に形成するのではなく、これらをPSA自体中に緊密に
混合することによる位置調整可能なPSA被覆ラミネート
の製造方法が開示されている。接着剤に配合する前に好
適な溶剤中にシロキサンポリマーまたはコポリマーの
「プレーミキシング」が推奨されている。この場合に
も、必要とする混合または分散および推奨されているプ
レミキシングには追加の工程が加わる。この数示のシロ
キサン添加剤は、接着剤本体全体に分散された小ビーズ
または小滴の形態であり、従って幾らかの小滴はラミネ
ートの接着剤/剥離シート界面(すなわち、PSA表面)
に位置し、基材上の初期位置調整作用をすると述べられ
ている。接着剤量の損失を最小にするが、得られたラミ
ネートは少量の損失であっても位置調整性の予想水準を
示さないブロックコポリマーまたは高分子量(25,000以
上)ポリシロキサンのいずれかの使用がU.K.P.NO 1,54
1,311およびU.S.P.NO.4,151,319に提案されている。
USP NO.4,151,319 (United Merchant and Manufactur
ers, Inc.) has a PS coating of polysiloxane or polysiloxane-polyoxyalkylene block copolymer.
A method of making a positionable PSA coated laminate is disclosed by intimately mixing them into the PSA itself, rather than forming them on the A side. It is recommended to "premix" the siloxane polymer or copolymer in a suitable solvent prior to compounding with the adhesive. In this case, too, additional steps are added to the required mixing or dispersion and the recommended premixing. This numbered siloxane additive is in the form of beadlets or droplets dispersed throughout the adhesive body, so some of the droplets are at the adhesive / release sheet interface (ie, PSA surface) of the laminate.
, And is said to have an initial position adjusting action on the substrate. UKPNO uses either block copolymers or high molecular weight (> 25,000) polysiloxanes to minimize the loss of adhesive volume but the resulting laminates do not show the expected level of alignability with small losses 1,54
Proposed in 1,311 and USP No. 4,151,319.

U.S.P.NO.4,346,189(Morgan Adhesive Company)に
は、異なる種類の用途におけるポリシロキサン添加剤
(約10,000までの分子量の)の使用が記載されている。
シリコーンを粘着性付与合成ゴム基剤PSA組成物と混合
し、かような組成物を被覆したシートを切断した場合の
縁からの漏出または流出を減少させている。非反応性ま
たは反応性ポリシロキサンのいずれも使用でき、接着剤
の他の成分に吸収されまたはグラフトされるか他の未知
の反応が行なわれ所望効果が得られるようであると述べ
られている。しかし、シリコーンは物質の接着特性に不
利な影響を及ぼすことなく比較的高濃度(6〜10%固形
分)まで添加できると述べられている。
USP No. 4,346,189 (Morgan Adhesive Company) describes the use of polysiloxane additives (of molecular weight up to about 10,000) in different types of applications.
Silicone is mixed with a tackifying synthetic rubber based PSA composition to reduce edge leakage or bleeding when sheets coated with such composition are cut. It is stated that either non-reactive or reactive polysiloxanes can be used and are likely to be absorbed or grafted onto other components of the adhesive or to carry out other unknown reactions to obtain the desired effect. However, it is stated that silicones can be added to relatively high concentrations (6-10% solids) without adversely affecting the adhesive properties of the material.

Y.Yamashita等による一連の論文、〔Polymer Bulletin.
.289(1982);Polymer Bulletin 10.368(1983);Mak
romol.Chem.185.9(1984);Macromolecules 18 580(19
85)〕に、記述されているように、幾らかのシリコーン
を含有するグラフトコポリマーの表面特性の改良のため
の使用が増加している。かような使用は、表面に対して
永続する疎水性(または親水性)付与のための添加剤と
してのグラフトコポリマーの使用に関する1982年11月4
日公告、日本国特許出願NO.57-179246のような最近の日
本の技術に反映されている。
A series of papers by Y. Yamashita et al. [Polymer Bulletin.
7 .289 (1982); Polymer Bulletin 10 .368 (1983); Mak
romol.Chem 185 .9 (1984);. Macromolecules 18 580 (19
85)], the use of graft copolymers containing some silicones for improving the surface properties is increasing. Such use relates to the use of the graft copolymer as an additive for imparting a permanent hydrophobic (or hydrophilic) property to the surface, 4 November 1982.
It is reflected in recent Japanese technologies such as Japanese publication, Japanese patent application No. 57-179246.

1983年10月3日公告、日本国特許出願NO.58-167606およ
び1983年9月14日公告、58-154766には、シリコーング
ラフトコポリマーの製造およびペイントフィルムのよう
な被覆組成物におけるこれらのコポリマーの使用が記載
されている。この場合、コポリマーは永続する撥水性、
撥油性、耐汚染性および減少した摩擦性を付与すると云
われている。1984年5月7日公告の日本国特許出願NO.5
9-78236には、表面処理剤としてのグラフトコポリマー
製造に使用するためのモノ官能性重合性シリコーンモノ
マー、すなわち、マクロモノマーの製造方法が開示され
ている。この場合も永続する撥水性および撥油性、耐汚
染性および低摩擦性を付与するためのかようなシリコー
ンマクロモノマーグラフトコポリマーの使用が、1984年
7月21日公告の日本国特許出願NO.59-126478に開示され
ている。本発明の譲受人に譲渡されたU.S.P.NO.4,728,5
71には、PSA被覆シート物質用およびPSA被覆テープの裏
側用の剥離被覆組成物としての非粘着性ポリシロキサン
−グラフトコポリマー(および他のポリマー物質との混
合物)の使用が開示されている。
Published October 3, 1983, Japanese Patent Application No. 58-167606 and Published September 14, 1983, 58-154766, describe the preparation of silicone graft copolymers and their copolymers in coating compositions such as paint films. The use of is described. In this case, the copolymer has a permanent water repellency,
It is said to impart oil repellency, stain resistance and reduced friction. Japanese patent application No. 5 announced on May 7, 1984
9-78236 discloses a process for preparing monofunctional polymerizable silicone monomers, ie macromonomers, for use in preparing graft copolymers as surface treatment agents. Again, the use of such silicone macromonomer graft copolymers to impart lasting water and oil repellency, stain resistance and low friction is disclosed in Japanese Patent Application No. 59- It is disclosed in 126478. USP NO. 4,728,5 assigned to the assignee of the present invention
71 discloses the use of non-stick polysiloxane-graft copolymers (and mixtures with other polymeric materials) as release coating compositions for PSA coated sheet materials and backsides of PSA coated tapes.

U.S.P.NO.4,693,935には、ポリシロキサン−グラフトコ
ポリマー感圧接着剤組成物およびこれを被覆したシート
物質が教示されている。本発明は、特に感圧接着剤およ
びこれを被覆した物品に関する。
USP No. 4,693,935 teaches polysiloxane-graft copolymer pressure sensitive adhesive compositions and sheet materials coated therewith. The invention particularly relates to pressure sensitive adhesives and articles coated therewith.

本発明の要約 本発明によって、室温(20℃)で接着剤であり、かつ、
ペンダントフルオロケミカル基およびペンダントポリシ
ロキサングラフトの両者を有するコポリマーから成る組
成物が提供される。同様なポリマーであるが比較的低い
Tg(ガラス転移温度)および異なる好ましいモノマーを
有するポリマーは、ペンダントポリシロキサングラフト
を含有し、接着剤組成物の層の露出表面を初期に比較的
低い度合の接着性を持たせ、一時的に「低接着フロント
サイズ」(low adhesive front size)の効果を付与し
ている。しかし、適用後に先行技術(U.S.P.4,693,93
5)におけるペンダントポリシロキサングラフトは層本
体に移行し、かつ、接着面が強い接着性を形成する接着
性を示すようである。従って、感圧接着剤組成物の一時
的の化学的表面改質は、感圧接着剤の被覆を有する物品
の位置調整適性が先行技術の前記した多くの障害なしに
可能なように行われる。しかし、本発明は感圧接着特性
に変化が得られるようにモノマーのわずかに異なる組合
せおよび割合が選ばれるコポリマーを利用し、従ってポ
リマーは化粧品および薬物の適用と同様にガラス、セラ
ミックス、金属並びに木材に対する表面仕上げ用として
良好な局所適用接着特性を有することが見出されてい
る。ポリマーはまた紙および木材のような多孔質物質用
の封止用組成物としても使用できる。
SUMMARY OF THE INVENTION According to the present invention, an adhesive at room temperature (20 ° C.), and
A composition is provided that comprises a copolymer having both pendant fluorochemical groups and pendant polysiloxane grafts. Similar polymer but relatively low
Polymers with Tg (glass transition temperature) and different preferred monomers contain pendant polysiloxane grafts to give the exposed surface of the layer of adhesive composition an initially relatively low degree of adhesion, temporarily The effect of "low adhesive front size" is given. However, after application, the prior art (USP 4,693,93
It seems that the pendant polysiloxane graft in 5) migrates to the layer body and that the adhesive surface shows strong adhesiveness. Thus, a temporary chemical surface modification of the pressure sensitive adhesive composition is performed so that the repositionability of the article having the pressure sensitive adhesive coating is possible without many of the obstacles mentioned above in the prior art. However, the present invention utilizes copolymers in which slightly different combinations and proportions of the monomers are chosen so as to obtain changes in pressure sensitive adhesive properties, so that the polymers can be used in glass, ceramics, metals and wood as well as cosmetic and drug applications. It has been found to have good topically applied adhesive properties for surface finishing against. The polymer can also be used as a sealing composition for porous materials such as paper and wood.

本発明のコポリマー中へのポリシロキサンの化学的配合
によってシロキサン損失が防止される。従って、各種の
組成物用として予想し得る度合の溶解度および接着性が
確実に得られる。
Chemical incorporation of the polysiloxane into the copolymer of the present invention prevents siloxane loss. Thus, a predictable degree of solubility and adhesion for various compositions is reliably obtained.

本発明の非感圧組成物は、20.0℃および0.5kg/cm2圧力
で本来非粘着性であるコポリマーから成る。組成物が室
温感圧組成物の場合には20.0℃よりはるかに低いTgで
も、もちろん、十分である。コポリマーの主鎖には、約
500以上(好ましくは約500〜約50,000、最も好ましくは
約5,000〜約25,000)の数平均分子量を有する一価シロ
キサンポリマー部分がこれにグラフトしている。
The non-pressure sensitive composition of the present invention consists of a copolymer that is inherently non-tacky at 20.0 ° C. and 0.5 kg / cm 2 pressure. A Tg well below 20.0 ° C. is, of course, sufficient if the composition is a room temperature pressure sensitive composition. The backbone of the copolymer contains approximately
Grafted with monovalent siloxane polymer moieties having a number average molecular weight of 500 or greater (preferably about 500 to about 50,000, most preferably about 5,000 to about 25,000).

さらに特別には、本発明の好ましい非粘着感圧接着剤組
成物は次の要素: (a)組成物が少なくとも20.0℃、好ましくは30.0℃、
最も好ましくは40.0℃のガラス転移温度を有し、かつ、 Aが全モノマーの全重量の少なくとも0.1〜約99%存在
し、1,1−ジヒドロパーフルオロアルカノール(または
弗素化もしくは非弗素化メチレンまたはアルキル同族体
のような同族体)、ω−ヒドリドフルオロアルカノー
ル、フルオロアルキルスルホンアミドアルコール、環状
フルオロアルキルアルコールおよびフルオロエーテルア
ルコールの遊離基重合性アクリルまたはメタクリルエス
テルの少なくとも1種であり; Bが全モノマーの全重量の少なくとも約0.01〜最大30重
量%の量で存在し、Aと共重合性の少なくとも1種の強
化用モノマーであり; Cが全モノマーの0.01〜50重量%存在し、一般式 X(Y)nSi(R)3-mZm 〔式中、XはAおよびBモノマーと共重合性ビニル基で
あり; Yは二価結合基(例えば1〜30炭素原子のアルキレン、
アリーレン、アルカリーレンおよびアラルキレン)であ
り、かつ、エステル、アミド、ウレタン、尿素基と一体
化するモノマーであり; nは0または1であり; mは1〜3の整数であり; Rは水素、低級アルキル(例えば1〜4炭素原子のメチ
ル、エチル、またはプロピル)、アリール(例えば6〜
20炭素原子のフェニル、または置換フェニル)またはア
ルコキシ(好ましくは1〜4炭素原子の低級アルコキ
シ)であり; Zは共重合条件下で本質的に非反応性であり、約500以
上の数平均分子量を有する一価シロキサンポリマー部分
である〕を有するモノマーであり; Dは少なくとも1種の遊離基重合性アクリレートまたは
メタクリレートモノマー(メチル部分が任意であること
を示すために以後「(メト)アクリレート」を使用す
る)である。〔好ましくは(メト)アクリレートはアク
リレート自体以外のペンダント基がアルキル、フェニ
ル、アルキルフェニル、フェニルアルキルなどのような
炭化水素基を示す。例としては、イソオクチルメタクリ
レート、イソペンチルメタクリレート、イソブチルメタ
クリレート、メチルメタクリレート、2−エチルヘキシ
ルアクリレート、イソノニルメタクリレートなどのよう
なアルコールの低〜中間(C1〜C12)(メト)アクリル
酸エステルである。〕 反復A,CおよびB並びに所望によりDモノマーから成る
コポリマー(モノマーを共重合させてCモノマーをグラ
フトさせて有するポリマー主鎖を形成する); (b)所望により、コポリマー10部当り約500部までの
薬物、または皮膚もしくは毛髪柔軟化またはコンディシ
ョニング成分;および (c)コポリマー10部当り約500部までの相溶性溶剤ま
たは可塑剤 から成る。
More particularly, preferred non-tacky pressure sensitive adhesive compositions of the present invention have the following components: (a) the composition is at least 20.0 ° C, preferably 30.0 ° C.
Most preferably it has a glass transition temperature of 40.0 ° C. and A is present in at least 0.1 to about 99% of the total weight of all monomers, 1,1-dihydroperfluoroalkanol (or fluorinated or non-fluorinated methylene or Homologs such as alkyl homologs), ω-hydrido fluoroalkanols, fluoroalkyl sulfonamide alcohols, at least one free radical polymerizable acrylic or methacrylic ester of cyclic fluoroalkyl alcohols and fluoroether alcohols; Is present in an amount of at least about 0.01 to a maximum of 30% by weight, based on the total weight of, of at least one reinforcing monomer copolymerizable with A; (Y) n Si (R) 3-m Z m [wherein, X is a vinyl group copolymerizable with A and B monomers; Y is a divalent bonding group (E.g. alkylene of 1 to 30 carbon atoms,
Arylene, alkali-arylene and aralkylene) and a monomer which is integrated with an ester, amide, urethane or urea group; n is 0 or 1; m is an integer of 1 to 3; R is hydrogen; Lower alkyl (eg, methyl, ethyl, or propyl of 1-4 carbon atoms), aryl (eg, 6-
20 carbon atom phenyl, or substituted phenyl) or alkoxy (preferably 1-4 carbon atom lower alkoxy); Z is essentially non-reactive under copolymerization conditions and has a number average molecular weight of about 500 or more. Is a monovalent siloxane polymer moiety having D; and D is at least one free radical polymerizable acrylate or methacrylate monomer (hereinafter "(meth) acrylate" to indicate that the methyl moiety is optional). Use). [Preferably (meth) acrylate has a pendant group other than the acrylate itself which represents a hydrocarbon group such as alkyl, phenyl, alkylphenyl and phenylalkyl. Examples are low to intermediate (C 1 -C 12 ) (meth) acrylic acid esters of alcohols such as isooctyl methacrylate, isopentyl methacrylate, isobutyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, isononyl methacrylate and the like. . Copolymers consisting of repeats A, C and B and optionally D monomers (monomers are copolymerized to graft C monomers to form a polymer backbone having); (b) optionally about 500 parts per 10 parts copolymer. Up to about 500 parts of a compatible solvent or plasticizer per 10 parts of copolymer; and (c) up to about 500 parts of a compatible solvent or plasticizer.

本発明によって、被覆組成物を木材、紙、金属、ガラ
ス、ポリマーおよび薬物、コンディショニングまたは柔
軟化成分を含有する組成物を体の少なくとも主要表面の
一つに適用することを含む動物体のような各種の表面へ
の適用方法も提供される。本発明によって特定の部類の
添加物を有する組成物から成る特定の生成物も提供され
る。
According to the present invention, such as an animal body comprising applying a coating composition containing wood, paper, metal, glass, polymers and drugs, conditioning or softening ingredients to at least one of the major surfaces of the body. Methods of application to various surfaces are also provided. The present invention also provides a particular product consisting of a composition having a particular class of additives.

本発明の詳細な説明 本発明のコポリマーは、ペンダントフルオロケミカル基
および少重量%のポリシロキサングラフトの添加によっ
て化学的に改質されているメタクリルまたはアクリルポ
リマー主鎖を有し、確立された構造を有する。かような
コポリマーを動物体の露出区域または動物の毛髪を被覆
したとき、非粘着性被覆または局部的適用を審美的かつ
快適にこれらの体に施すことができる。表面に適用した
後は、組成物は組成物中に加えた活性成分の存在を維持
することができる。
DETAILED DESCRIPTION OF THE INVENTION The copolymers of the present invention have a methacrylic or acrylic polymer backbone that has been chemically modified by the addition of pendant fluorochemical groups and a small percentage by weight of polysiloxane grafts to establish an established structure. Have. When such copolymers coat exposed areas of animal bodies or animal hair, non-stick coatings or topical applications can be applied aesthetically and comfortably to these bodies. After application to the surface, the composition is capable of maintaining the presence of active ingredients added to the composition.

コポリマー接着剤組成物の表面特性は、グラフトシロキ
サンポリマー部分の分子量およびコポリマーの全シロキ
サン含量の両者を変化させることによって化学的に要求
通りに製造することができ、比較的高いシロキサン含量
および(または)分子量を使用すれば比較的低い初期接
着力が得られる。コポリマーの(メト)アクリルポリマ
ー主鎖の化学的性質および分子量は、基材に対する接着
の度合を特定の用途の要求に適合させるように選択する
こともできる。これらのシロキサン含量は比較的低いか
ら、本発明のコポリマーは例えば、ビニルまたはメタク
リル主鎖を有するポリマー組成物のようなシロキサンを
含まないポリマーと容易に相溶性になる。
The surface properties of the copolymer adhesive composition can be made chemically as desired by varying both the molecular weight of the grafted siloxane polymer moieties and the total siloxane content of the copolymer, and relatively high siloxane content and / or The use of molecular weight results in relatively low initial adhesion. The chemistry and molecular weight of the (meth) acrylic polymer backbone of the copolymer can also be selected to match the degree of adhesion to the substrate to the requirements of a particular application. The relatively low content of these siloxanes makes the copolymers of the present invention readily compatible with siloxane-free polymers such as, for example, polymer compositions having a vinyl or methacrylic backbone.

本発明の組成物の好ましい製造方法では、必要または所
望ならば重合溶媒から直接被覆することができる高純度
のグラフトコポリマーが得られる。得られた被覆は、硬
化または架橋の必要はない。しかし、剪断強さまたは耐
溶剤性もしくは光化学または酸化力に対する耐性の増加
が所望ならば、輻射線硬化(電子ビームまたは紫外線)
または化学的架橋のような当業界において周知の方法に
よって架橋させることもできる。
The preferred method of making the compositions of the present invention provides high purity graft copolymers that can be coated directly from the polymerization solvent, if necessary or desired. The resulting coating does not need to be cured or crosslinked. However, if increased shear strength or solvent resistance or resistance to photochemistry or oxidizing power is desired, radiation curing (electron beam or ultraviolet).
Alternatively, it may be crosslinked by a method well known in the art such as chemical crosslinking.

シロキサンポリマー部分は、主鎖上に位置する反応性部
位にモノマーを重合させる。予め形成したポリマー部分
を主鎖の部位に結合させる、または好ましくはアクリル
またはメタクリルモノマーAと極性モノマーBおよび予
備形成したポリマー状シロキサンモノマーCとを共重合
させることによってグラフトできる。ポリマー状シロキ
サン表面改質剤は化学的に結合しているから、本発明の
組成物を特定の度合の凝集性および溶解度を有するよう
に化学的に製造することができ、一貫して再生産でき
る。
The siloxane polymer moiety polymerizes the monomer into reactive sites located on the backbone. It can be grafted by attaching preformed polymer moieties to the sites of the backbone or preferably by copolymerizing acrylic or methacrylic monomer A with polar monomer B and preformed polymeric siloxane monomer C. Because the polymeric siloxane surface modifier is chemically bonded, the compositions of the present invention can be chemically manufactured to have a certain degree of cohesiveness and solubility and can be consistently reproduced. .

前記したように、本発明の組成物は室温(20.0℃)およ
び中程度の圧力(0.5kg/cm2)で本来非粘着性である
(メト)アクリレートコポリマーから成る。約500以上
の数平均分子量を有する一価シロキサンポリマー部分を
コポリマー主鎖にグラフトさせる。コポリマーは好まし
くは上記の説明によるA,BおよびCモノマー並びに所望
によるDモノマーの共重合反復単位から本質的に成る。
As mentioned above, the composition of the present invention consists of a (meth) acrylate copolymer that is inherently tack free at room temperature (20.0 ° C.) and moderate pressure (0.5 kg / cm 2 ). Monovalent siloxane polymer moieties having a number average molecular weight of about 500 or greater are grafted to the copolymer backbone. The copolymer preferably consists essentially of copolymerized repeating units of A, B and C monomers according to the above description and optionally D monomers.

Aモノマー(1種以上存在できる)は、A(またはAお
よびB)の重合後に非粘着性物質が得られるように選択
する。Aモノマーの代表的例は1,1−ジヒドロパーフル
オロアルカノール(1)および同族体(2)のアクリル
酸またはメタクリル酸エステルである: 1 CF3(CF2)xCH2OH 2 CF3(CF2)x(CH2)yOH w−ヒドロフルオロアルカノール3、 xは0〜20であり、 yは少なくとも1および10までである。
The A monomer (one or more of which may be present) is selected so that a non-sticky material is obtained after polymerization of A (or A and B). Representative examples of A monomers are acrylic or methacrylic acid esters of 1,1-dihydroperfluoroalkanol (1) and homologues (2): 1 CF 3 (CF 2 ) x CH 2 OH 2 CF 3 (CF 2 ) x (CH 2 ) y OH w-hydrofluoroalkanol 3, x is 0-20 and y is at least 1 and up to 10.

3 HCF3(CF2)x(CH2)yOH フルオロアルキルスルホンフミドアルコール4、 xは0〜20であり、 yは少なくとも1および10までである。3 HCF 3 (CF 2 ) x (CH 2 ) y OH Fluoroalkylsulfone fumido alcohol 4, x is 0-20 and y is at least 1 and up to 10.

環状フルオロアルキルアルコール5、 xは0〜20であり、 R1は20炭素原子までのアルキルまたはアリールアルキル
または6環炭素原子までのシクロアルキルである。
Cyclic fluoroalkyl alcohol 5, x is 0-20, R 1 is alkyl or arylalkyl up to 20 carbon atoms or cycloalkyl up to 6 ring carbon atoms.

およびフルオロエーテルアルコール6および7、 zは0〜7であり yは少なくとも1および10までである 6 CF3(CF2CF2-Oq(CF2O)x(CH2)yOH qは2〜20であり、そしてxより大きく、xは0〜20で
あり、yは少なくとも1そして10までである。
And fluoroether alcohols 6 and 7, z is 0 to 7 and y is at least 1 and 10 6 CF 3 (CF 2 CF 2 —O q (CF 2 O) x (CH 2 ) y OH q is 2 -20 and greater than x, x is 0-20 and y is at least 1 and up to 10.

pおよびsは少なくとも1であり、rは1〜6である。 p and s are at least 1 and r is 1-6.

好ましい重合Aモノマー主鎖組成物にはフルオロアクリ
レート8〜13が含まれる。
Preferred polymerized A monomer backbone compositions include fluoroacrylates 8-13.

極性モノマー、Bの代表的例には、アクリル酸、メタク
リル酸、イタコン酸、アクリルアミド、メタクリルアミ
ド、N,N−ジメチルアクリルアミド、アクリロニトリ
ル、メタクリロニトリル、およびN−ビニルピロリドン
が含まれる。親水性「B」モノマーは、一般式: CH2=CR2-CO-L-R3-(OH)d (式中、R2はH、メチル、エチル、シアノまたはカルボ
キシメチルであり、LはO、NHであり、dは1〜3であ
り、そして、R3は1〜12炭素原子を含有する原子価d+
1のヒドロカルビル基である)によって表わされるモノ
−または多官能性ヒドロキシ基含有分子でもよい。この
部類の好ましいモノマーは、ヒドロキシエチル(メト)
アクリレート、ヒドロキシプロピル(メト)アクリレー
ト、ヒドロキシブチル(メト)アクリレート、グリセロ
ールモノ(メト)アクリレート、トリス(ヒドロキシメ
チル)エタンモノアクリレート、ペンタエリトリトール
モノ(メト)アクリレート、N−ヒドロキシメチル(メ
ト)アクリルアミド、ヒドロキシエチル(メト)アクリ
ルアミドおよびヒドロキシプロピル(メト)アクリルア
ミドである。
Representative examples of polar monomers, B, include acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, acrylonitrile, methacrylonitrile, and N-vinylpyrrolidone. Hydrophilic “B” monomers have the general formula: CH 2 ═CR 2 —CO—LR 3 — (OH) d where R 2 is H, methyl, ethyl, cyano or carboxymethyl, L is O, NH, d is 1 to 3, and R 3 is a valence d + containing 1 to 12 carbon atoms.
Mono- or polyfunctional hydroxy group-containing molecule represented by 1 is a hydrocarbyl group). A preferred monomer in this class is hydroxyethyl (meth)
Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, tris (hydroxymethyl) ethane monoacrylate, pentaerythritol mono (meth) acrylate, N-hydroxymethyl (meth) acrylamide, hydroxy Ethyl (meth) acrylamide and hydroxypropyl (meth) acrylamide.

親水性モノマー「B」は、一般式: CH2=CR2-CO-L-R3-(NR4R5)d (式中、R2,L,R3およびdは上記の定義と同じであり、
そして、R4およびR5は水素または1〜12炭素原子のアル
キル基であり、またはこれらは一緒に環状または複素環
式基を構成する)モノ−または多官能性アミノ基含有分
子の部類に属することができる。この部類の好ましいモ
ノマーは、アミノエチル(メト)アクリレート、アミノ
プロピル(メト)アクリレート、N,N−ジメチルアミノ
エチル(メト)アクリレート、N,N−ジエチルアミノエ
チル(メト)アクリレート、N,N−ジメチルアミノプロ
ピル(メト)アクリルアミド、N−イソプロピルアミノ
プロピル(メト)アクリルアミドおよび4−メチル−1
−アクリロイル−ピペラジンである。
The hydrophilic monomer "B" has the general formula: CH 2 = CR 2 -CO-LR 3- (NR 4 R 5 ) d (wherein R 2 , L, R 3 and d are the same as defined above). ,
And R 4 and R 5 are hydrogen or an alkyl group of 1 to 12 carbon atoms, or they together form a cyclic or heterocyclic group) belong to the class of mono- or polyfunctional amino group-containing molecules be able to. Preferred monomers in this class are aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino. Propyl (meth) acrylamide, N-isopropylaminopropyl (meth) acrylamide and 4-methyl-1
-Acryloyl-piperazine.

親水性「B」モノマーは、メトキシエチル(メト)アク
リレート、2(2−エトキシエトキシ)エチル(メト)
アクリレート、ポリエチレングリコールモノ(メト)ア
クリレートまたはポリプロピレングリコールモノ(メ
ト)アクリレートのようなアルコキシ置換(メト)アク
リレートまたは(メト)アクリルアミドでもよい。
The hydrophilic "B" monomer is methoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth).
It may also be an alkoxy-substituted (meth) acrylate or (meth) acrylamide such as acrylate, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate.

特に有用な「B」モノマーは、一般式: CH2=CR2-CO-L-R3-(N+R4R5R6)dQ- (式中、R2,R3,R4,R5,Lおよびdは上記の定義と同じで
あり、R6は水素または1〜12炭素原子のアルキルであ
り、そしてQは有機または無機アニオンである)の置換
または未置換アンモニウム基を有するモノマーである。
かようなモノマーの好ましい例は、2−N,N,N−トリメ
チルアンモニウムエチル(メト)アクリレート、2−N,
N,N−トリエチルアンモニウムエチル(メト)アクリレ
ート、3−N,N,N−トリメチルアンモニウムプロピル
(メト)アクリレート、N(2−N′,N′,N′−トリメ
チルアンモニウム)エチル(メト)アクリルアミド、N
−(ジメチルヒドロキシエチルアンモニウム)プロピル
(メト)アクリルアミドなどであり、対イオンはクロラ
イド、ブロマイド、アセテート、プロピオネート、ラウ
レート、パルミテート、ステアレートなどでよい。モノ
マーは有機または無機対イオンのN,N−ジメチルジアリ
ルアンモニウム塩でもよい。
Particularly useful "B" monomer has the general formula: CH 2 = CR 2 -CO- LR 3 - (N + R 4 R 5 R 6) d Q - ( wherein, R 2, R 3, R 4, R 5 , L and d are as defined above, R 6 is hydrogen or alkyl of 1 to 12 carbon atoms, and Q is an organic or inorganic anion) and is a monomer having a substituted or unsubstituted ammonium group. is there.
Preferred examples of such monomers include 2-N, N, N-trimethylammonium ethyl (meth) acrylate, 2-N,
N, N-triethylammoniumethyl (meth) acrylate, 3-N, N, N-trimethylammoniumpropyl (meth) acrylate, N (2-N ', N', N'-trimethylammonium) ethyl (meth) acrylamide, N
-(Dimethylhydroxyethylammonium) propyl (meth) acrylamide and the like, and the counter ion may be chloride, bromide, acetate, propionate, laurate, palmitate, stearate and the like. The monomer may be an N, N-dimethyldiallylammonium salt of an organic or inorganic counterion.

アンモニウム基含有ポリマーは、「B」モノマーとして
上記の任意のアミノ基含有モノマーを使用し、ペンダン
トアミノ基が実質的にプロトン化されるpHまで、得られ
たポリマーを有機または無機酸によって酸性化すること
によっても製造できる。全部置換されたアンモニウム基
含有ポリマーは、上記のアミノポリマーを、アルキル化
基でアルキル化することによって製造できる;この方法
はMenschutkin反応として当業界において一般的に公知
である。
Ammonium group-containing polymers use any of the amino group-containing monomers described above as the "B" monomer and acidify the resulting polymer with an organic or inorganic acid to a pH at which the pendant amino groups are substantially protonated. It can also be manufactured. Fully substituted ammonium group containing polymers can be prepared by alkylating the above amino polymers with alkylating groups; this method is generally known in the art as the Menschutkin reaction.

本発明の親水性「B」モノマーは、ビニルスルホン酸、
スチレンスルホン酸、2−アクリルアミド−2−メチル
プロパンスルホン酸、アリルオキシベンゼンスルホン酸
などのようなスルホン酸基含有モノマーでもよい。これ
らのモノマーはモノマーとしてプロトン化酸型で使用で
き、得られた相当するポリマーを有機および無機塩基で
中和して塩形態のポリマーを得る。
The hydrophilic "B" monomer of the present invention is vinyl sulfonic acid,
It may be a sulfonic acid group-containing monomer such as styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyloxybenzene sulfonic acid and the like. These monomers can be used in the protonated acid form as monomers and the corresponding polymers obtained are neutralized with organic and inorganic bases to give salt-form polymers.

親水性「B」モノマーは、ビニルピリジン、ビニルイミ
ダゾール、ビニルベンズイミダゾール、ビニルアズラク
トン、ビニルフランなどのような他のアルケニル複素環
化合物でもよい。これらの複素環式コモノマーでは極性
基材と水素結合する部位が得られ、かつ、かような基材
に対する得られたポリマーの接着性が改良される。
The hydrophilic "B" monomer may also be other alkenyl heterocycles such as vinyl pyridine, vinyl imidazole, vinyl benzimidazole, vinyl azlactone, vinyl furan and the like. These heterocyclic comonomers provide sites for hydrogen bonding with polar substrates and improve the adhesion of the resulting polymers to such substrates.

好ましい「B」モノマーは、アクリル酸、N,N−ジメチ
ルアクリルアミド、メタクリル酸、およびN−ビニルピ
ロリドンである。Bモノマーの重量による量は、ポリマ
ーの過度の硬さを避けるように全モノマーの全重量の約
30%を超えないことが好ましい。約2〜約25重量%のB
モノマーの配合が最も好ましく、かつ、高い凝集または
内部強さ、極性表面に対する良好な接着性並びに良好な
物理的性質も保留している組成物が得られる。
Preferred "B" monomers are acrylic acid, N, N-dimethylacrylamide, methacrylic acid, and N-vinylpyrrolidone. The amount by weight of B-monomer is about about the total weight of all monomers to avoid excessive hardness of the polymer.
It is preferred not to exceed 30%. About 2 to about 25 wt% B
Compositions are obtained in which the incorporation of monomers is most preferred and retains also high cohesion or internal strength, good adhesion to polar surfaces as well as good physical properties.

好ましいCモノマーは、一般式: (式中、R7は水素原子またはCOOH基であり、R8は水素原
子、メチル基またはCH2COOH基である)を有するX基を
有するものとさらに定義することができる。
Preferred C monomers have the general formula: It can be further defined as having an X group having R 7 is a hydrogen atom or a COOH group and R 8 is a hydrogen atom, a methyl group or a CH 2 COOH group.

CモノマーのZ基は一般式: 〔式中、R9およびR11は独立に、低級アルキル、アリー
ルまたはフルオロアルキルであり、この場合、低級アル
キルおよびフルオロアルキルの両者は1〜3個の炭素原
子を有するアルキル基を示し、アリールはフェニルまた
は置換フェニル(20個までの炭素原子の)を示す。R10
はアルキル(1〜20炭素原子の)、アルコキシ(1〜20
炭素原子の)、アルキルアミノ(1〜20炭素原子の)、
アリール(20炭素原子までの)、ヒドロキシルまたはフ
ルオロアルキル(1〜20炭素原子の)であり、そしてe
は約5〜約700の整数である〕を有する。好ましくはC
モノマーは、 (b)X-Si(R)3-mZm (式中、mは1、2または3であり、gは0または1で
あり、R11はアルキル(1〜10炭素原子の)または水素
であり、fは2〜6の整数であり、hは0〜2の整数で
あり、そしてX,RおよびZは上記の定義と同じである)
から成る群から選ばれる一般式を有する。
The Z group of the C monomer has the general formula: [Wherein, R 9 and R 11 are independently lower alkyl, aryl or fluoroalkyl, in which case both lower alkyl and fluoroalkyl represent an alkyl group having 1 to 3 carbon atoms, and aryl is Denotes phenyl or substituted phenyl (up to 20 carbon atoms). R 10
Is alkyl (1 to 20 carbon atoms), alkoxy (1 to 20 carbon atoms)
Carbon atoms), alkylamino (1-20 carbon atoms),
Aryl (up to 20 carbon atoms), hydroxyl or fluoroalkyl (1-20 carbon atoms), and e
Is an integer of about 5 to about 700]. Preferably C
The monomer is (B) X-Si (R) 3-m Z m ; (In the formula, m is 1, 2 or 3, g is 0 or 1, R 11 is alkyl (of 1 to 10 carbon atoms) or hydrogen, f is an integer of 2 to 6, and h Is an integer from 0 to 2 and X, R and Z are the same as defined above)
Having a general formula selected from the group consisting of:

本発明の局所組成物は、A,BおよびC並びに所望により
Dモノマーを共重合させ、次に、必要または所望ならば
組成物の最終実用性を最適化するため相溶性化粧品、ま
たは医療的に活性成分と混合することによって得られ
る。
The topical compositions of the present invention are copolymerized with A, B and C, and optionally D monomers, and then compatible cosmetically or medically to optimize the final utility of the composition if necessary or desired. Obtained by mixing with the active ingredient.

上記の組成物を組成物中における適切な割合で皮膚また
は毛髪に被覆した場合、組成物が乾燥したとき粘着性は
観察されない。約500以下の分子量を有するCモノマー
を含有するコポリマーは、皮膚上での実在性または永続
する保留を得るにはあまり有効ではない。50,000以上の
分子量を有するCモノマーを含有するコポリマーでは実
在性が有効に付与されるが、かような高分子量では、共
重合工程の間残余のモノマーとCモノマーとの起り得る
非相溶性のためCの配合量の減少が起る。従って、約50
0〜約50,000の範囲のCモノマーの分子量が好ましい。
約5,000〜約25,000の分子量範囲が最も好ましい。
When the above composition is applied to the skin or hair in a suitable proportion in the composition, no tackiness is observed when the composition is dried. Copolymers containing C monomers having a molecular weight of about 500 or less are not very effective in obtaining a real or permanent retention on the skin. Copolymers containing C-monomers having a molecular weight of 50,000 or more effectively provide realism, but at such high molecular weights due to possible incompatibilities between residual monomers and C-monomers during the copolymerization process. A decrease in the compounding amount of C occurs. Therefore, about 50
Molecular weights of C monomer ranging from 0 to about 50,000 are preferred.
Most preferred is the molecular weight range of about 5,000 to about 25,000.

所望の性質を得るためには、Cモノマーは全モノマー重
量の約0.01〜約50%の量でコポリマーに配合するのが好
ましい。含ませるCモノマーの量は、特定の用途によっ
て変化し得るが、上記に特定した範囲内の分子量を有す
るCモノマーの前記のような比率での配合は円滑に進行
し、かつ、各種の用途に対して有効な実在性が得られ、
同時に価格的にも有効であることが見出されている。
To obtain the desired properties, the C monomer is preferably incorporated into the copolymer in an amount of about 0.01 to about 50% by total monomer weight. The amount of the C monomer to be contained may vary depending on the specific application, but the C monomer having the molecular weight within the above-specified range in the above ratio can be smoothly blended, and various amounts can be used for various applications. Effective reality is obtained,
At the same time, it has been found to be price effective.

BおよびCモノマーの全重量は、好ましくは、コポリマ
ー中の全モノマーの全重量の約0.01〜約70%の範囲内で
ある。
The total weight of B and C monomers is preferably in the range of about 0.01 to about 70% of the total weight of all monomers in the copolymer.

本発明のCモノマーは、単一官能基(ビニル、エチレン
状不飽和、アクリロイルまたはメタクリロイル基)を有
し、時々マクロモノマーまたは「マクロマー」(macrom
er)と呼ばれる末端に官能基を有するポリマーである。
かようなモノマーは公知であり、U.S.P.NOS,3,786,116
および3,842,059に記載されているようなMilkovich等に
よって開示されている方法によって製造できる。ポリジ
メチルシロキサンマクロモノマーの製造およびビニルモ
ノマーとの引続く共重合は、Y.Yamashita等によって数
種の論文:[Polymer J.14,913(1982);ACS Polymer P
reprints 25(1),245.(1984);Makromol.Chem.185,9
(1984)]に記載されている。マクロモノマー製造のこ
の方法には、ヘキサメチルシクロトリシロキサンモノマ
ー(D3)をアニオン重合させ、制御された分子量のリビン
グポリマーを形成し、重合性ビニル基を含有するクロロ
シラン化合物によって停止させる工程が含まれる。モノ
官能性シロキサンマクロモノマーとビニルモノマーとの
遊離基重合によって十分に確立された構造、すなわち、
グラフトシロキサン分枝の制御された長さおよび数を有
するシロキサン−グラフトコポリマーが得られる。
The C-monomers of the present invention have a single functional group (vinyl, ethylenically unsaturated, acryloyl or methacryloyl groups) and are sometimes macromonomers or "macromers".
er) is a polymer having a terminal functional group.
Such monomers are known and are described in USPNOS, 3,786,116.
And the method disclosed by Milkovich et al., As described in 3,842,059. The production of polydimethylsiloxane macromonomers and their subsequent copolymerization with vinyl monomers has been reported by Y. Yamashita et al. In several papers: [Polymer J. 14 , 913 (1982); ACS Polymer P
reprints 25 (1), 245. (1984); Makromol. Chem. 185 , 9
(1984)]. The method of macromonomer preparation, hexamethylcyclotrisiloxane monomer (D 3) was subjected to anionic polymerization, to form a living polymer of controlled molecular weight, include the step of stopping the chlorosilane compound containing a polymerizable vinyl group Be done. A well-established structure by free radical polymerization of monofunctional siloxane macromonomers and vinyl monomers, namely
A siloxane-graft copolymer having a controlled length and number of grafted siloxane branches is obtained.

上記のアニオン重合に使用するのに適しているモノマー
は、一般に、式 (式中、R9およびR11は前記の定義と同じであり、eは
3〜7の整数である)のジオルガノシクロシロキサンで
ある。好ましいのはeが3または4であり、R9およびR
11の両者がメチルである環状シロキサンであり、これら
の環状シロキサンを以後それぞれD3およびD4と称する。
歪んだ(Strained)環構造であるD3特にに好ましい。
Suitable monomers for use in the above anionic polymerization generally have the formula Wherein R 9 and R 11 are as defined above and e is an integer from 3 to 7). Preferred is when e is 3 or 4, R 9 and R
Both of 11 are cyclic siloxanes in which both are methyl, and these cyclic siloxanes are hereinafter referred to as D 3 and D 4 , respectively.
Particularly preferred is D 3 which is a strained ring structure.

アニオン重合の開始剤は、モノ官能性リビングポリマー
が得られるように選択する。好適な開始剤には、アルキ
ルまたはアリール基中に20個まで、またはそれ以上炭素
原子、さらに好ましくは8個までの炭素原子を含有する
アルキルまたはアリールリチウム、ナトリウムまたはカ
リウム化合物のようなアルカリ金属炭化水素が含まれ
る。かような化合物の例は、エチルナトリウム、プロピ
ルナトリウム、フェニルナトリウム、ブチルカリウム、
オクチルカリウム、メチルリチウム、エチルリチウム、
n−ブチルリチウム、sec−ブチルリチウム、t−ブチ
ルリチウム、フェニルリチウム、および2−エチルヘキ
シルリチウムである。開始剤としてリチウム化合物が好
ましい。同様に好適な開始剤はアルカリ金属アルコキシ
ド、ヒドロキシドおよびアミド並びに式: (式中、Mはアルカリ金属、テトラアルキルアンモニウ
ムまたはテトラアルキルホスホニウムカチオンであり、
そしてR9,R10およびR11は上記の定義と同じである)の
トリオルガノシラノレートである。好ましいトリオルガ
ノシラノレート開始剤は、リチウムメチルシラノレート
(LTMS)である。一般に、歪んだ環状モノマーおよびリ
チウム開始剤の両者の好ましい使用は、再分布反応の可
能性を減少させ、それによって望ましくない環状オリゴ
マーが合理的に無い狭い分子量分布のシロキサンマクロ
モノマーが得られる。
The initiator of anionic polymerization is selected so that a monofunctional living polymer is obtained. Suitable initiators include alkyl or aryl containing up to 20 or more carbon atoms, more preferably up to 8 carbon atoms in an alkyl or aryl group, such as alkali metal carbonization compounds such as lithium, sodium or potassium compounds. Contains hydrogen. Examples of such compounds are ethyl sodium, propyl sodium, phenyl sodium, butyl potassium,
Octyl potassium, methyl lithium, ethyl lithium,
n-butyllithium, sec-butyllithium, t-butyllithium, phenyllithium, and 2-ethylhexyllithium. Lithium compounds are preferred as initiators. Similarly suitable initiators are alkali metal alkoxides, hydroxides and amides and of the formula: (In the formula, M is an alkali metal, a tetraalkylammonium or a tetraalkylphosphonium cation,
And R 9 , R 10 and R 11 are the same as defined above). A preferred triorganosilanolate initiator is lithium methylsilanolate (LTMS). In general, the preferred use of both distorted cyclic monomers and lithium initiators reduces the likelihood of redistribution reactions, thereby resulting in narrow molecular weight distribution siloxane macromonomers reasonably free of undesirable cyclic oligomers.

分子量は開始剤/環状モノマー比によって決定され、従
って、開始剤の量はモノマー1モル当り約0.004〜約0.4
モルのオルガノ金属開始剤と変化できる。好ましくは、
この量はモノマー1モル当り約0.008〜約0.04モルの開
始剤量であろう。
The molecular weight is determined by the initiator / cyclic monomer ratio, so the amount of initiator is about 0.004 to about 0.4 per mole of monomer.
Can vary with moles of organometallic initiator. Preferably,
This amount will be about 0.008 to about 0.04 moles of initiator per mole of monomer.

アニオン重合の開始剤には、不活性の、好ましくは極性
有機溶剤が使用できる。リチウム対イオンでのアニオン
重合生長反応には、テトラヒドロフラン、ジメチルスル
ホオキシドまたはヘキサメチル燐トリアミドのような強
い極性溶剤またはかような極性溶剤とヘキサン、ヘプタ
ン、オクタン、シクロヘキサンまたはトルエンのような
非極性脂肪族、脂環式または芳香族炭化水素溶剤との混
合物のいずれかを必要とする。極性溶剤は、生長反応を
可能にするシラノレートイオンを「活性化」するのに役
立つ。
An inert, preferably polar organic solvent can be used as the initiator of the anionic polymerization. Anionic polymerization growth reactions with lithium counterions include strong polar solvents such as tetrahydrofuran, dimethylsulfoxide or hexamethylphosphortriamide or such polar solvents and non-polar aliphatics such as hexane, heptane, octane, cyclohexane or toluene. , Either with cycloaliphatic or aromatic hydrocarbon solvents. The polar solvent serves to “activate” the silanolate ions that allow the growth reaction.

一般に、重合は約−50℃〜約100℃、好ましくは約−20
℃〜約30℃の範囲の温度で行なわれる。無水条件および
窒素、ヘリウムまたはアルゴンのような不活性雰囲気が
必要である。
Generally, the polymerization is about -50 ° C to about 100 ° C, preferably about -20 ° C.
C. to about 30.degree. C. at temperatures. Anhydrous conditions and an inert atmosphere such as nitrogen, helium or argon are required.

アニオン重合の停止は、一般に、リビングポリマーアニ
オンとハロゲン含有停止剤、すなわち、官能化されたク
ロロシランとの直接反応によって行い、ビニル末端基重
合体モノマーを製造する。かような停止剤は、一般式:
X(Y)n(R)3-mClm(式中、mは1、2または3であり、X,
Y,nおよびRは前記の定義と同じである)によって表わ
すことができる。好ましい停止剤は、メタクリルオキシ
プロピルジメチルクロロシランである。停止反応は、重
合温度でリビングポリマーに僅かにモル過剰の停止剤
(開始剤量に関して)を添加することによって行なわれ
る。Y.Yamashita等の前記の論文によれば、マクロモノ
マーの官能性を高めるために停止剤添加後に反応混合物
に超音波を放射してもよい。マクロモノマーの精製はメ
タノールの添加によって行う。
Termination of anionic polymerization is generally carried out by direct reaction of a living polymer anion with a halogen-containing terminating agent, i.e. a functionalized chlorosilane, to produce a vinyl terminated polymer monomer. Such terminators have the general formula:
X (Y) n (R) 3-m Cl m (wherein m is 1, 2 or 3, X,
Y, n and R are the same as defined above). The preferred terminating agent is methacryloxypropyl dimethylchlorosilane. The termination reaction is carried out by adding a slight molar excess of terminating agent (relative to the amount of initiator) to the living polymer at the polymerization temperature. According to the aforementioned article by Y. Yamashita et al., Ultrasonic waves may be radiated to the reaction mixture after addition of a terminating agent to enhance the functionality of the macromonomer. Purification of the macromonomer is performed by adding methanol.

Dモノマーの代表的例は、アルコールが1〜12炭素原
子、好ましくは1〜8炭素原子を有し、炭素原子の平均
数が約4〜12個であるメタノール、エタノール、1−プ
ロパノール、2−プロパノール、1−ブタノール、1,1
−ジメチルエタノール、2−メチル−1−プロパノー
ル、1−ペンタノール、2−ペンタノール、3−ペンタ
ノール、2−メチル−1−ブタノール、3−メチル−1
−ブタノール、2−ヘキサノール、2−メチル−1−ペ
ンタノール、3−メチル−1−ペンタノール、シクロヘ
キサノール、2−エチル−1−ブタノール、3−ヘプタ
ノール、ベンジルアルコール、2−オクタノール、6−
メチル−1−ヘプタノール、2−エチル−1−ヘキサノ
ール、3,5−ジメチル−1−ヘキサノール、3,5,5−トリ
メチル−1−ヘキサノール、1−デカノール、および1
−ドデカノールなどのようなアルコールの低級〜中級メ
タクリル酸エステルを含む(全モノマーの50%まで)こ
とができる。非第三アルコールの使用が好ましい。少量
の非重合性スチレン、ビニルエステル、ビニルクロライ
ド、ビニリデンクロライド、アクリロイルモノマーなど
が使用できる。これらのモノマーは、最終ポリマー組成
物のTgを少なくとも20.0℃、好ましくは30.0℃、最も好
ましくは少なくとも40℃に維持するのを妨げてはならな
い。かようなモノマーは当業界において公知であり、か
つ、多数のものが商用として入手できる。好ましい重合
Dモノマー主鎖組成物には、ポリ(イソオクチルメタク
リレート)、ポリ(イソノニルメタクリレート)、ポリ
(2−エチルヘキシルメタクリレート)、ポリイソペン
チルメタクリレート、ポリ(n−ブチルメタクリレー
ト)、ポリ(イソブチルメタクリレート)、ポリ(メチ
ルメタクリレート)およびこれらと他のDモノマーとの
コポリマーが含まれる。幾らかの量のアクリレートも存
在できるが、これらの組成物が感圧性にならない程度の
量である。
Representative examples of D-monomers are methanol, ethanol, 1-propanol, 2-, wherein the alcohol has 1-12 carbon atoms, preferably 1-8 carbon atoms and the average number of carbon atoms is about 4-12. Propanol, 1-butanol, 1,1
-Dimethyl ethanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1
-Butanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-
Methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, and 1
It may comprise lower to intermediate methacrylic acid esters of alcohols such as dodecanol and the like (up to 50% of the total monomers). The use of non-tertiary alcohols is preferred. A small amount of non-polymerizable styrene, vinyl ester, vinyl chloride, vinylidene chloride, acryloyl monomer, etc. can be used. These monomers should not prevent the T g of the final polymer composition from being maintained at least 20.0 ° C, preferably 30.0 ° C, most preferably at least 40 ° C. Such monomers are known in the art, and many are commercially available. Preferred polymerized D monomer backbone compositions include poly (isooctyl methacrylate), poly (isononyl methacrylate), poly (2-ethylhexyl methacrylate), polyisopentyl methacrylate, poly (n-butyl methacrylate), poly (isobutyl methacrylate). ), Poly (methylmethacrylate) and copolymers of these with other D monomers. Although some amount of acrylate can be present, it is such that these compositions are not pressure sensitive.

Aモノマー、BモノマーおよびCモノマー並びに所望の
Dモノマーの共重合は、UlrichによるU.S.再発行特許N
o.24,906に記載されているように慣用の遊離基重合によ
って行なわれる。モノマーを不活性有機溶剤に溶解さ
せ、熱的または光化学的のいずれかで活性化される好適
な遊離基開始剤を使用して重合させる。好適な熱活性化
開始剤には、2,2′−アゾビス(イソブチロニトリル)
のようなアゾ化合物、t−ブチルハイドロパーオキサイ
ドのようなハイドロパーオキサイド、ベンゾイルパーオ
キサイドまたはシクロヘキサノンパーオキサイドのよう
な過酸化物が含まれ、そして、好適な光化学的活性開始
剤には、ベンゾフェノン、ベンゾインエチルエーテルお
よび2,2−ジメトキシ−2−フェニルアセトフェノンが
含まれる。使用される開始剤の量は、一般に、全重合性
組成物の約0.01〜約5重量%である。
Copolymerization of the A, B and C monomers and the desired D monomer is described by Ulrich in US Reissue Patent N
by conventional free radical polymerization as described in o.24,906. The monomers are dissolved in an inert organic solvent and polymerized using a suitable free radical initiator that is activated either thermally or photochemically. Suitable heat-activated initiators include 2,2'-azobis (isobutyronitrile)
Azo compounds such as, hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide or cyclohexanone peroxide, and suitable photochemically active initiators include benzophenone, Benzoin ethyl ether and 2,2-dimethoxy-2-phenylacetophenone are included. The amount of initiator used is generally about 0.01 to about 5% by weight of the total polymerizable composition.

遊離基共重合に使用する有機溶剤は、反応体および生成
物に対して不活性であり、かつ、反応に他の不利な影響
を与えない任意の有機液体でよい。好適な溶剤には、エ
チルアセテートおよびエチルアセテートとトルエンまた
はヘプタンとトルエンおよびイソプロピルアルコールと
の混合物が含まれる。他の溶剤系も使用できる。溶剤の
量は、一般に、反応体と溶剤との全重量の約30〜80重量
%である。溶液重合に加えて、共重合は、懸濁、エマル
ション、および塊状重合のような他の周知の方法によっ
て行うことができる。
The organic solvent used for free radical copolymerization may be any organic liquid that is inert to the reactants and products and that does not otherwise adversely affect the reaction. Suitable solvents include ethyl acetate and mixtures of ethyl acetate and toluene or heptane and toluene and isopropyl alcohol. Other solvent systems can also be used. The amount of solvent is generally about 30-80% by weight of the total weight of reactants and solvent. In addition to solution polymerization, copolymerization can be carried out by other well known methods such as suspension, emulsion and bulk polymerization.

前記したように、好ましいグラフト化法には制御された
分子量のメタクリルモノマー,A、強化用モノマー,Bおよ
び化学的に特別に製造したマクロモノマー、C並びに所
望によるモノマーDの共重合が含まれる。各々が最終生
成物の性質のある程度の予想可能性が得られる他のグラ
フト化法も使用できる。別法の一つは、メタクリルポリ
マー主鎖を予備形成し、次に、この予備形成主鎖と環状
シロキサンモノマーとを共重合させる方法である。他の
方法は予備形成モノ官能性シロキサンポリマーを予備形
成メタクリルポリマー主鎖にグラフトさせる方法であ
る。これらおよび他のポリマーグラフト化法は、Noshay
およびMcGrathにより、Block Copolymers,Academic Pr
ess,New York(1977).13〜16頁に、そしてさらに詳細
には、BattaerdおよびTregearにより、Graft Copolyme
rs,J.Wiley and Sons,New York(1967)に記載されてい
る。
As mentioned above, the preferred grafting method involves the copolymerization of methacrylic monomers of controlled molecular weight, A, reinforcing monomers, B and chemically specially prepared macromonomers, C and optionally monomer D. Other grafting methods may also be used, each of which gives some predictability of the properties of the final product. One alternative is to preform a methacrylic polymer backbone and then copolymerize the preformed backbone with a cyclic siloxane monomer. Another method is to graft the preformed monofunctional siloxane polymer onto the preformed methacrylic polymer backbone. These and other polymer grafting methods are available from Noshay.
And McGrath, Block Copolymers , Academic Pr
ess, New York (1977). 13-16, and more particularly by Battaerd and Tregear, Graft Copolyme.
rs , J. Wiley and Sons, New York (1967).

溶液または分散体における本発明の局所適用コポリマー
組成物は、頭の毛髪のような一次外皮系でない好適な体
の部分に容易に被覆できる。組成物は残存する毛(顔、
腕および脚の毛のような)には適用できるが本発明の実
施において毛髪の一次処理は考えていない。これらはま
た、目または鼻孔の内張処理用には好ましくない。非水
棲哺乳類の体の非粘膜部分には特に好ましく、人間以外
の動物の毛皮処理も好ましい(犬、猫、家兎など)。他
の適切な添加物を含む組成物は、接着剤、有機または無
機表面用のコンディショニング処理、および木材または
紙の封止剤として使用できる。
The topical application copolymer compositions of the present invention in solution or dispersion can be readily coated onto suitable body parts that are not the primary integumentary system, such as head hair. The composition contains residual hair (face,
However, primary treatment of the hair is not considered in the practice of the invention, although it can be applied to hair (such as the hair of the arms and legs). They are also not preferred for lining the eyes or nostrils. It is particularly preferred for non-mucosal parts of the body of non-aquatic mammals, and fur treatment of non-human animals is also preferred (dogs, cats, rabbits, etc.). Compositions with other suitable additives can be used as adhesives, conditioning treatments for organic or inorganic surfaces, and as wood or paper sealants.

本発明の組成物は、ワイピング、吹付、手塗り、棉棒塗
りなどのような任意の各種の被覆方法によって被覆でき
る。
The composition of the present invention can be coated by any of various coating methods such as wiping, spraying, hand coating, cotton bar coating and the like.

皮膚に対する薬物の局所適用は、フィルム、テープのよ
うな自立性凝集性物品または粉末、軟膏、クリーム、ロ
ーションなどの直接適用にまさる提案された改良法とし
てのプラスター(plaster)を使用して伝統的に実施さ
れてきた。これらの比較的実質的媒体では、哺乳動物の
皮膚または毛に対して医薬品の比較的持続性かつ制御し
うる適用が得られることが感じられた。しかし、これら
の医療用途ではそれら自体の問題に悩まされている。フ
ィルムおよびテープのすべては、運動の間体の外面が受
ける伸長、曲げ、しわにこれらが完全に適合できないた
め不快になる傾向がある。フィルム、テープおよびプラ
スターは、特に見える顔および手に適用したとき、美容
上受入れ難い。フィルムおよびテープは、不注意な接触
またはフィルムまたはテープの下で起こる発汗によって
皮膚から一部または全部が容易、かつ、思いがけず脱落
する。これは適用の医療的効果を直接減少させる。フィ
ルムおよびテープは表面に向う湿分を止める、これは医
療的にも不利であり、かつ、表面に対する酸素の透過を
阻止する。うすいポリマーの適用は容易に破れ医薬品の
送出が阻害されるためこれらの問題の解決策とはならな
い。
Topical application of drugs to the skin is traditionally done using plaster as a proposed improvement over self-supporting cohesive articles such as films, tapes or direct application of powders, ointments, creams, lotions and the like. Has been carried out. It has been felt that these relatively substantial vehicles provide a relatively lasting and controllable application of the drug to the skin or hair of mammals. However, these medical applications suffer from their own problems. All films and tapes tend to be uncomfortable due to their inability to perfectly accommodate the stretching, bending, and wrinkles that the outer surface of the body experiences during exercise. Films, tapes and plasters are cosmetically unacceptable, especially when applied to the visible face and hands. Films and tapes easily and unexpectedly fall off the skin in part or in whole due to inadvertent contact or sweating underneath the film or tape. This directly reduces the medical effect of application. Films and tapes stop moisture towards the surface, which is medically disadvantageous and prevents the permeation of oxygen to the surface. The application of thin polymers is not a solution to these problems as they are easily broken and interfere with drug delivery.

本発明において、薬物の適正な選択および溶液、エマル
ションまたは分散体中における非感圧接着性ポリマーバ
インダーの選択によって、薬物の極めて有効な局所適用
および皮膚治療および人間以外の動物の毛皮の毛の処理
が行えることが見出された。常識とは異なり、割合は特
に非粘膜域の皮膚上にバインダーおよび薬物の非凝集
性、非粘着性被覆が形成されるように選択する。
In the present invention, by the proper choice of drug and the choice of non-pressure sensitive adhesive polymer binder in solution, emulsion or dispersion, highly effective topical application of drug and skin treatment and treatment of non-human animal fur hair. It was found that Contrary to common sense, the proportions are chosen such that a non-cohesive, non-adhesive coating of binder and drug is formed, especially on non-mucosal skin.

本発明の実施の場合の薬物は、直接的の薬効または神経
学的効果(アルコールを除く)を有する化合物または物
質である。細菌、かび、またはウイルスの生長、増殖ま
たは生き残りに対して有利な活性を有する物質または抗
ヒスタミン、抗毒素、麻酔薬、鎮痛剤、止痒剤、ビタミ
ンおよび炎症抑制剤である物質も薬物の用語に含める。
これらの物質は医療業界において周知であり、従って、
詳細な表は不要と考える。代表的化合物には、酢酸ヒド
ロコーチゾン、ウンデシレン酸、トルナフテート、メチ
ルサリチレート、リドカイン、オキシテトラサイクリン
・HCl、レチノイン酸、MinoxidilRなどが含まれる。こ
れらの薬物は適用部位または皮膚を通して吸収されて医
薬品活性を付与する。
A drug in the practice of the present invention is a compound or substance that has a direct pharmacological or neurological effect (excluding alcohol). Also included in the term drug are substances that have an advantageous activity on the growth, growth or survival of bacteria, fungi or viruses or substances that are antihistamines, antitoxins, anesthetics, analgesics, antipruritics, vitamins and anti-inflammatory agents. include.
These substances are well known in the medical industry and therefore
I don't think a detailed table is necessary. Representative compounds include hydrocortisone acetate, undecylenic acid, tolnaftate, methyl salicylate, lidocaine, oxytetracycline.HCl, retinoic acid, Minoxidil R and the like. These drugs are absorbed through the site of application or the skin to impart pharmaceutical activity.

これらの薬物は本発明の臨界割合で油相溶性非感圧接着
剤と組合せる。感圧接着剤は、標準部類の物質として認
められている技術である。これらは乾燥状態で(残留溶
剤を除いて実質的に無溶剤である)で室温(15.0〜25.0
℃)で旺盛、かつ、永久粘着性であり、手の圧力以上を
必要としない単なる接触によって各種の表面に強固に接
着する。これらは紙、セロファン、ガラス、木材および
金属のような物質に対する強い接着保持力を及ぼすため
に水、溶剤または熱による活性化を必要としない。これ
らは十分な凝集力保持並びに弾性を有するため、これら
の強力な粘着性にも拘らずこれらは指で取扱うことがで
き、かつ、実質的に残留物を残すことなく平滑な表面か
ら除去できる(Test Method Pressure-Sensitive Tape
s.6th Ed.Pressure-Sensitive Tape Council,1953.参
照)。感圧接着剤およびテープは周知であり、かつ、か
ような接着剤における所望性質の広い範囲並びにバラン
スは十分に分析されている(U.S.P.No.4,374,883;およ
Treatise on Adhesion and Adhesives Vol.2,「Mater
eals」、R.I.Patrick,Ed.Marcel Dekker.Inc.N.Y.1969
における「Pressure-Sensitive Adhesives」を参照)感
圧接着剤として有用な各種の物質および組成物が商用と
して入手でき、かつ、文献に完全に論議されている(例
えば、HouwinkおよびSalomon.Adhesion and Adhesives,
Elsevier Publ.CO.Amsterdam,Netherland.1967;Handboo
k of Pressure-Sensitive Adhesive Technology,Donate
s Satas.Ed.,Van Nostrand Reinhold CO.N.Y.1982)。
These drugs are combined with the oil compatible non-pressure sensitive adhesive in the critical proportion of the present invention. Pressure sensitive adhesives are a technology recognized as a standard class of substance. They are dry (substantially solvent-free except for residual solvent) at room temperature (15.0-25.0
It is viscous at ℃) and is permanently tacky, and firmly adheres to various surfaces by simple contact without requiring more than hand pressure. They do not require water, solvent or heat activation to exert a strong adhesive hold on materials such as paper, cellophane, glass, wood and metals. Since they have sufficient cohesive strength retention and elasticity, despite their strong tackiness, they can be handled with the fingers and removed from smooth surfaces with virtually no residue left ( Test Method Pressure-Sensitive Tape
s.6th Ed.Pressure-Sensitive Tape Council, 1953.). Pressure sensitive adhesives and tapes are well known, and the wide range and balance of desired properties in such adhesives has been well analyzed (USP No. 4,374,883; and Treatise on Adhesion and Adhesives). Vol.2, `` Mater
eals '', RI Patrick, Ed. Marcel Dekker. Inc. NY1969
Various materials and compositions useful as pressure sensitive adhesives are commercially available and are fully discussed in the literature (e.g., Houwink and Salomon. Adhesion and Adhesives ,
Elsevier Publ.CO.Amsterdam, Netherland.1967; Handboo
k of Pressure-Sensitive Adhesive Technology, Donate
S Satas.Ed., Van Nostrand Reinhold CO.NY1982).

感圧接着剤は、一般に、化学的に、ゴム−樹脂物質、ア
クリル樹脂、ポリウレタン樹脂、シリコーン樹脂などか
ら成る。感圧接着剤配合における組成物および改良法が
記載されている各種の特許引例には、U.S.再発行特許N
o.24,906;U.S.P.Nos.2,652,351;3,740,366;3,299,010;
3,770,708;3,701,758;3,922,464;3,931,087;4,012,560;
4,077,926;4,387,172;4,418,120;4,629,663;などがあ
る。これらの部類のゴム樹脂、アクリル、シリコーンお
よびポリウレタン感圧接着剤並びに任意の他の感圧接着
剤は、本発明においては一般に有用でない。本発明の詳
細な割合において非感圧接着剤のみが使用され、そし
て、薬物の非粘着性適用が得られる。本発明において有
用なポリマーは、油相溶性(有機油および非極性溶媒中
に分散性、膨潤性または可溶性)であり、かつ、一般に
それらの性質は明らかに疎水性である。
Pressure sensitive adhesives are generally chemically composed of rubber-resin materials, acrylic resins, polyurethane resins, silicone resins and the like. Various patent references describing compositions and improvements in pressure sensitive adhesive formulations include US Reissue Patent N
o.24,906; USP Nos. 2,652,351; 3,740,366; 3,299,010;
3,770,708; 3,701,758; 3,922,464; 3,931,087; 4,012,560;
4,077,926; 4,387,172; 4,418,120; 4,629,663; and so on. These classes of rubber resins, acrylic, silicone and polyurethane pressure sensitive adhesives and any other pressure sensitive adhesives are generally not useful in the present invention. In the detailed proportions of the invention only non-pressure sensitive adhesives are used and non-stick application of the drug is obtained. Polymers useful in the present invention are oil compatible (dispersible, swellable or soluble in organic oils and non-polar solvents), and generally their properties are clearly hydrophobic.

組成物に使用されるポリマーの分子量は、広い範囲に変
化し得る。分子量は要求される接着効果を付与するため
に適した大きさでなければならない。上限は配合物の要
求事項によってのみ決定される。分子量の増加に伴い、
ポリマーは粘稠になりすぎて美容的に魅力ある組成物の
製造が困難になる。16.6%非揮発物で測定したとき、Br
ookfield粘度が50〜100,000cps.好ましくは500〜15,000
の間の値を有するポリマーが、一般に本発明の組成物に
おいて有用であろう。
The molecular weight of the polymers used in the composition can vary over a wide range. The molecular weight should be of suitable size to provide the required adhesive effect. The upper limit is determined only by the formulation requirements. As the molecular weight increases,
The polymer becomes too viscous, making it difficult to produce cosmetically attractive compositions. When measured with 16.6% non-volatiles, Br
ookfield viscosity of 50-100,000 cps, preferably 500-15,000
Polymers having values in between will generally be useful in the compositions of the present invention.

本組成物において有用なアクリレートポリマーは、水に
不溶性であり、かつ、弱いおよび中程度の水素結合溶剤
中において約6〜10の間の溶解パラメータを有する。ポ
リマーの溶解パラメータ範囲および溶剤の広範な表(弱
い水素結合、中程度水素結合または強い水素結合のいず
れかに分類されている)が、Polymer Handbook(Bandru
pおよびImmergut編)IV-344〜358頁に記載されている。
必要な溶解パラメータを有するアクリレートポリマー
は、組成物の油基剤中に可溶性、膨潤性または分散性で
ある。
The acrylate polymers useful in the present compositions are insoluble in water and have solubility parameters in weak and moderate hydrogen bonding solvents of between about 6-10. An extensive table of polymer solubility parameter ranges and solvents (classified as either weak, medium, or strong hydrogen bonds) can be found in the Polymer Handbook (Bandru).
p and Immergut ed.) IV-344-358.
Acrylate polymers with the required solubility parameters are soluble, swellable or dispersible in the oil base of the composition.

本発明の組成物には3種の基本型;すなわち、油型、水
中油型および油中水型がある。油配合物は、基油、ポリ
マーおよび活性成分(例えば、薬物)を一緒に混合し、
混合物を緩くかく拌しながら約60℃(140°F)に加温
することによって製造される。水相成分がエマルジョン
配合物の一部である場合には、一緒にして82℃(180°
F)に加熱する。この相を82℃で徐々に油相成分に添加
し、混合物をかく拌しながら冷却させる。配合物は、一
般に、約0.5〜10重量%のアクリレートポリマーを含有
し、好ましい範囲は約0.5〜5.0重量%である。0.25%以
下の量では、ポリマーは皮膚が水にさらされたとき有意
量の活性成分(薬物のような)を保持するのに効果が少
なくなる。10%以上の量では、配合物には一般に、粘着
性になり、不快な感触が現われる。
There are three basic types of compositions of the present invention; oil type, oil-in-water type and water-in-oil type. The oil formulation comprises a base oil, a polymer and an active ingredient (eg, drug) mixed together,
It is prepared by warming the mixture to about 60 ° C (140 ° F) with gentle stirring. If the water phase components are part of the emulsion formulation, combine them together at 82 ° C (180 ° C)
Heat to F). This phase is slowly added to the oil phase ingredients at 82 ° C and the mixture is allowed to cool with stirring. The formulations generally contain from about 0.5 to 10% by weight of acrylate polymer with a preferred range of about 0.5 to 5.0% by weight. At amounts below 0.25%, the polymer is less effective at retaining a significant amount of active ingredient (such as a drug) when the skin is exposed to water. Above 10%, the formulations generally become tacky and have an unpleasant feel.

使用する場合の組成物の化粧油基剤は、固体または液体
でよいが、全配合物は適用が容易なために皮膚温度で幾
分流動性であるべきである。香料、充填剤、染料、着色
剤、防腐剤、酸化防止剤および他のかような物質は、組
成物の実体性に影響を与えない少量で組成物に含ませる
ことができる。
The cosmetic oil base of the composition, if used, may be solid or liquid, but the entire formulation should be somewhat fluid at skin temperature for ease of application. Perfumes, fillers, dyes, colorants, preservatives, antioxidants and other such substances can be included in the composition in small amounts that do not affect the substance of the composition.

人間の皮膚に適用したとき、これらの生成物は皮膚の表
面にフィルムを形成する。中に分散されているポリマー
は、薬物または化学的処置を皮膚上に保持し、それによ
ってポリマーのない組成物より有意に大きい薬理学的ま
たは美容上の利点が得られる。
When applied to human skin, these products form a film on the surface of the skin. The polymer dispersed therein retains the drug or chemical treatment on the skin, thereby providing significantly greater pharmacological or cosmetic benefits than the polymer-free composition.

前記したように、哺乳類(一般に非水棲哺乳類)の局所
区域に適用するための組成物は、組成物の全重量の0.25
〜10重量%、好ましくは0.5〜5重量%、最も好ましく
は0.5〜2重量%のポリマーを含む。活性成分または薬
物は組成物の全重量の0.1〜50重量%の広い範囲、好ま
しくは0.25〜20重量%、さらに好ましくは0.5〜10重量
%、最も好ましくは1〜3重量%存在する。ポリマー:
薬物の比(wt.ポリマー/wt.薬物)は、本発明の利点を
達成するためには1/5〜1/50の範囲内でなければならな
い。
As mentioned above, a composition for application to a localized area of a mammal (generally a non-aquatic mammal) has a composition of 0.25% by total weight of the composition.
-10% by weight, preferably 0.5-5% by weight, most preferably 0.5-2% by weight of polymer. The active ingredient or drug is present in a wide range of from 0.1 to 50% by weight of the total composition, preferably from 0.25 to 20% by weight, more preferably from 0.5 to 10% by weight and most preferably from 1 to 3% by weight. polymer:
The drug ratio (wt. Polymer / wt. Drug) must be in the range of 1/5 to 1/50 to achieve the benefits of the present invention.

本発明のこれらおよび他の特徴を次の非限定実施例に示
す。
These and other features of the invention are shown in the following non-limiting examples.

実施例1 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)とN,N−ジメチルアクリルアミ
ド(DMA)および2(N−メチルパーフルオロオクタン
スルホンアミド)エチルメタクリレート(MeFOSEMA)と
の重合。
Example 1 Polymerization of methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) with N, N-dimethylacrylamide (DMA) and 2 (N-methylperfluorooctanesulfonamido) ethyl methacrylate (MeFOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のDMAおよび60
部のMeFOSEMAの混合物に0.5部のベンゾイルパーオキサ
イド(BPO)を添加した。この溶液を窒素でパージし、
窒素雰囲気下でビン中に密封した。ビンをAtlasLaunder
-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を蒸
発させることによってポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts DMA and 60 in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of parts MeFOSEMA 0.5 parts benzoyl peroxide (BPO) was added. Purge the solution with nitrogen,
Sealed in bottle under nitrogen atmosphere. Atlas Launder the bin
The polymer was recovered by heating in -O-Meter R for 48 hours at 60 ° C and evaporating the solvent under reduced pressure.

実施例2〜4 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)とN,N−ジメチルアクリルアミ
ド(DMA)、イソブチルメタクリレート(IBM)および2
(N−メチルパーフルオロオクタンスルホンアミド)エ
チルメタクリレート(MeFOSEMA)との重合。
Examples 2-4 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) with N, N-dimethylacrylamide (DMA), isobutyl methacrylate (IBM) and 2
Polymerization with (N-methylperfluorooctanesulfonamide) ethyl methacrylate (MeFOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のDMA、14〜45
部のIBM、15〜45部のMeFOSEMAの混合物に0.5部のベンゾ
イルパーオキサイド(BPO)を添加した。この溶液を窒
素でパージし、窒素雰囲気下でビンの中に密封した。ビ
ンをLaunder-O-MeterR中、60℃で48時間加熱し、減圧下
で溶剤を蒸発させることによってポリマーを回収した。
20 parts PDMS (MW = 20,000) in 200 parts ethyl acetate and 10 parts isopropanol, 20 parts DMA, 14-45
0.5 parts benzoyl peroxide (BPO) was added to a mixture of 15 parts IBM, 15-45 parts MeFOSEMA. The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. During Launder-O-Meter R a bottle, was heated at 60 ° C. 48 hours, the polymer was recovered by evaporation of the solvent under reduced pressure.

実施例5 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)とN,N−ジメチルアクリルアミ
ド(DMA)、イソブチルメタクリレート(IBM)および1,
1−ジヒドロパーフルオロオクチルメタクリレート(FOM
A)との重合。
Example 5 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) with N, N-dimethylacrylamide (DMA), isobutyl methacrylate (IBM) and 1,
1-dihydroperfluorooctyl methacrylate (FOM
Polymerization with A).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のDMA、30部のI
BMおよび30部のFOMAの混合物に0.5部のベンゾイルパー
オキサイド(BPO)を添加した。この溶液を窒素でパー
ジし、窒素雰囲気下でビン中に密封した。ビンをLaunde
r-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を除
去することによってポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts DMA, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts FOMA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Launde bottle
During and rO-Meter R, and heated at 60 ° C. 48 hours, the polymer was recovered by removing the solvent under reduced pressure.

実施例6 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)とN,N−ジメチルアクリルアミ
ド(DMA)、イソブチルメタクリレート(IBM)および2
(N−ブチルパーフルオロオクタンスルホンアミド)エ
チルアクリレート(BuFOSEA)との重合。
Example 6 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) with N, N-dimethylacrylamide (DMA), isobutyl methacrylate (IBM) and 2
Polymerization with (N-butylperfluorooctanesulfonamide) ethyl acrylate (BuFOSEA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のDMA、30部のI
BMおよび30部のBuFOSEAの混合物に0.5部のベンゾイルパ
ーオキサイド(BPO)を添加した。この溶液を窒素でパ
ージし、窒素雰囲気下でビン中に密封した。ビンをLaun
der-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を
蒸発させることによってポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts DMA, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts BuFOSEA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Laun the bottle
During der-O-Meter R, and heated at 60 ° C. 48 hours, the polymer was recovered by evaporation of the solvent under reduced pressure.

実施例7 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)とアクリル酸(AA)、イソブチ
ルメタクリレート(IBM)および2(N−メチルパーフ
ルオロオクタンスルホンアミド)エチルメタクリレート
(MeFOSEMA)との重合。
Example 7 Polymerization of Methacryloxypropyl-Terminated Polydimethylsiloxane Macromonomer (PDMS) with Acrylic Acid (AA), Isobutyl Methacrylate (IBM) and 2 (N-Methylperfluorooctane Sulfonamide) Ethyl Methacrylate (MeFOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、10部のAA、60部のIB
Mおよび10部のMeFOSEMAの混合物に0.5部のベンゾイルパ
ーオキサイド(BPO)を添加した。この溶液を窒素でパ
ージし、窒素雰囲気下でビン中に密封した。ビンをLaun
der-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を
蒸発させることによってポリマーを回収した。
20 parts PDMS (MW = 20,000) in 200 parts ethyl acetate and 10 parts isopropanol, 10 parts AA, 60 parts IB
To a mixture of M and 10 parts MeFOSEMA was added 0.5 part benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Laun the bottle
During der-O-Meter R, and heated at 60 ° C. 48 hours, the polymer was recovered by evaporation of the solvent under reduced pressure.

実施例8 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)と、N−ビニルピロリドン(NV
P)、イソブチルメタクリレート(IBM)および2(N−
メチルパーフルオロオクタンスルホンアミド)エチルメ
タクリレート(MeFOSEMA)との重合。
Example 8 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) and N-vinylpyrrolidone (NV
P), isobutyl methacrylate (IBM) and 2 (N-
Polymerization with methyl perfluorooctane sulfonamide) ethyl methacrylate (MeFOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のNVP、30部のI
BMおよび30部のMeFOSEMAの混合物に、0.5部のベンゾイ
ルパーオキサイド(BPO)を添加した。この溶液を窒素
でパージし、窒素雰囲気下でビン中に密封した。ビンを
Launder-O-MeterR中、60℃で48時間加熱し、減圧下で溶
剤を蒸発させることによってポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts NVP, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts MeFOSEMA, 0.5 parts benzoyl peroxide (BPO) was added. The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Bottle
During Launder-O-Meter R, and heated at 60 ° C. 48 hours, the polymer was recovered by evaporation of the solvent under reduced pressure.

実施例9 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)と、N−ビニルピロリドン(NV
P)、イソブチルメタクリレート(IBM)および2(N−
ブチルパーフルオロオクタンスルホンアミド)エチルア
クリレート(BuFOSEA)との重合。
Example 9 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) and N-vinylpyrrolidone (NV
P), isobutyl methacrylate (IBM) and 2 (N-
Polymerization with butyl perfluorooctane sulfonamide) ethyl acrylate (BuFOSEA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のNVP、30部のI
BMおよび30部のBuFOSEAの混合物に0.5部のベンゾイルパ
ーオキサイド(BPO)を添加した。この溶液を窒素でパ
ージし、窒素雰囲気下でビン中に密封した。ビンをLaun
der-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を
蒸発させてポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts NVP, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts BuFOSEA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Laun the bottle
During der-O-Meter R, and heated at 60 ° C. 48 hours to recover the solvent evaporated the polymer under reduced pressure.

実施例10 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)と、N−ビニルピロリドン(NV
P)、イソブチルメタクリレート(IBM)および1,1−ジ
ヒドロパーフルオロオクチルメタクリレート(FOMA)と
の重合。
Example 10 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) and N-vinylpyrrolidone (NV
Polymerization with P), isobutyl methacrylate (IBM) and 1,1-dihydroperfluorooctyl methacrylate (FOMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のNVP、30部のI
BM、および30部のFOMAの混合物に0.5部のベンゾイルパ
ーオキサイド(BPO)を添加した。この溶液を窒素でパ
ージし、窒素雰囲気下でビン中に密封した。ビンをLaun
der-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤を
蒸発させてポリマーを回収した。
20 parts PDMS (MW = 20,000), 20 parts NVP, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts FOMA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Laun the bottle
During der-O-Meter R, and heated at 60 ° C. 48 hours to recover the solvent evaporated the polymer under reduced pressure.

実施例11 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)と2−ビニル−4,4−ジメチル
−1,3−オキサゾリン−5−オン(VDM)、イソブチルメ
タクリレート(IBN)および2(N−メチルパーフルオ
ロオクタンスルホンアミド)エチルメタクリレート(Me
FOSEMA)との重合。
Example 11 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) and 2-vinyl-4,4-dimethyl-1,3-oxazoline-5-one (VDM), isobutyl methacrylate (IBN) and 2 (N- Methyl perfluorooctane sulfonamide) ethyl methacrylate (Me
Polymerization with FOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、20部のVDM、30部のI
BMおよび30部のMeFOSEMAの混合物に0.5部のベンゾイル
パーオキサイド(BPO)を添加した。この溶液を窒素で
パージし、窒素雰囲気中でビン中に密封した。ビンをLa
under-O-MeterR中、60℃で48時間加熱し、減圧下で溶剤
を蒸発させてポリマーを回収した。
20 parts PDMS (MW = 20,000), 200 parts VDM, 30 parts I in 200 parts ethyl acetate and 10 parts isopropanol.
To a mixture of BM and 30 parts MeFOSEMA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. La the bottle
The polymer was recovered by heating in an under-O-Meter R at 60 ° C for 48 hours and evaporating the solvent under reduced pressure.

実施例12 メタクリロキシプロピル−末端ポリジメチルシロキサン
マクロモノマー(PDMS)と、N−ビニルピロリドン(NV
P)、2−ビニル−4,4−ジメチル−1,3−オキサゾリン
−5−オン(VDM)、イソブチルメタクリレート(IBM)
および2(N−メチルパーフルオロオクタンスルホンア
ミド)エチルメタクリレート(MeFOSEMA)との重合。
Example 12 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) and N-vinylpyrrolidone (NV
P), 2-vinyl-4,4-dimethyl-1,3-oxazoline-5-one (VDM), isobutyl methacrylate (IBM)
And polymerization with 2 (N-methylperfluorooctanesulfonamido) ethyl methacrylate (MeFOSEMA).

200部のエチルアセテートおよび10部のイソプロパノー
ル中の20部のPDMS(MW=20,000)、15部のNVP、5部のV
DM、30部のIBM、および30部のMeFOSEMAの混合物に0.5部
のベンゾイルパーオキサイド(BPO)を添加した。この
溶液を窒素でパージし、窒素雰囲気下でビン中に密封し
た。ビンをLaunder-O-MeterR中、60℃で48時間加熱し、
減圧下で溶剤を蒸発させることによってポリマーを回収
した。
20 parts PDMS (MW = 20,000) in 200 parts ethyl acetate and 10 parts isopropanol, 15 parts NVP, 5 parts V
To a mixture of DM, 30 parts IBM, and 30 parts MeFOSEMA was added 0.5 parts benzoyl peroxide (BPO). The solution was purged with nitrogen and sealed in a bottle under nitrogen atmosphere. Heat bottle in Launder-O-Meter R at 60 ° C for 48 hours,
The polymer was recovered by evaporating the solvent under reduced pressure.

実施例13 分子量10,000のメタクリロキシプロピル−末端ポリジメ
チルシロキサンマクロモノマー(PDMS)とN−ビニルピ
ロリドン(NVP)、メチルメタクリレート(MMA)および
1,1−ヒドロパーフルオロオクチルメタクリレート(FOM
A)との重合。
Example 13 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) with molecular weight 10,000 and N-vinylpyrrolidone (NVP), methylmethacrylate (MMA) and
1,1-hydroperfluorooctyl methacrylate (FOM
Polymerization with A).

1000部のシクロヘキサン中の20部のPDMS、60部のMMA、1
0部のNVPおよび10部のFOMAの混合物に0.16部のアゾビス
(イソブチロニトリル)を添加した。この溶液を還流コ
ンデンサー、機械かく拌機および温度計を備えた150ml3
つ口フラスコに入れた。フラスコを窒素ガスでフラッシ
ュし、そして溶液を55℃で20時間加熱した。得られたポ
リマーはシクロヘキサン中には溶解しない固体塊を形成
した。
20 parts PDMS in 60 parts cyclohexane, 60 parts MMA, 1
To a mixture of 0 parts NVP and 10 parts FOMA was added 0.16 parts azobis (isobutyronitrile). 150 ml3 of this solution equipped with a reflux condenser, mechanical stirrer and thermometer
Placed in a one-necked flask. The flask was flushed with nitrogen gas and the solution heated at 55 ° C. for 20 hours. The resulting polymer formed a solid mass that did not dissolve in cyclohexane.

実施例14 分子量10,000のメタクリロキシプロピル−末端ポリジメ
チルシロキサンマクロモノマー(PDMS)と、N−ビニル
ピロリドン(NVP)、2−(N−メチルパーフルオロオ
クタンスルホンアミド)エチルアクリレート(MeFOSE
A)、メチルメタクリレート(MMA)およびアクリル酸
(AA)との重合。
Example 14 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) having a molecular weight of 10,000, N-vinylpyrrolidone (NVP), 2- (N-methylperfluorooctanesulfonamide) ethyl acrylate (MeFOSE)
Polymerization with A), methyl methacrylate (MMA) and acrylic acid (AA).

150部のメチルエチルケトン中の19部のPDMS、52部のMM
A、19部のNVP、5部のAAおよび5部のMeFOSEAの混合物
に0.25部のアゾビス(イソブチロニトリル)を添加し
た。この溶液を窒素ガスでパージし、窒素雰囲気下でビ
ン中に密封した。ビンをLaunder-O-MeterR中、55℃で16
時間加熱し、大気圧で溶剤を蒸発させることによってポ
リマーを回収した。
19 parts PDMS, 52 parts MM in 150 parts methyl ethyl ketone
To a mixture of A, 19 parts NVP, 5 parts AA and 5 parts MeFOSEA was added 0.25 parts azobis (isobutyronitrile). The solution was purged with nitrogen gas and sealed in a bottle under nitrogen atmosphere. Place bottles in Launder-O-Meter R at 55 ° C for 16
The polymer was recovered by heating for hours and evaporating the solvent at atmospheric pressure.

別個の実験において、150部のメチルエチルケトン中の1
9部のPDMS、43部のMMA、19部のNVP、5部のAAおよび14
部のMeFOSEMの混合物に、0.25部のアゾビス(イソブチ
ロニトリル)を添加した。この溶液を窒素ガスでパージ
し、窒素雰囲気下でビン中に密封した。ビンをLaunder-
O-MeterR中、55℃で16時間加熱し、大気圧で溶剤を蒸発
させることによってポリマーを回収した。
In a separate experiment, 1 in 150 parts methyl ethyl ketone
9 parts PDMS, 43 parts MMA, 19 parts NVP, 5 parts AA and 14
To a mixture of parts MeFOSEM was added 0.25 parts azobis (isobutyronitrile). The solution was purged with nitrogen gas and sealed in a bottle under nitrogen atmosphere. Launder-bin
During O-Meter R, heated for 16 hours at 55 ° C., and the polymer was recovered by evaporation of the solvent at atmospheric pressure.

実施例15 分子量20,000のメタクリロキシプロピル−末端ポリジメ
チルシロキサンマクロモノマー(PDMS)と、イソブチル
アクリレート(BA)、アクリル酸(AA)、および2−
(N−メチルパーフルオロオクタンスルホンアミド)エ
チルアクリレート(MeFOSEA)との重合。
Example 15 Methacryloxypropyl-terminated polydimethylsiloxane macromonomer (PDMS) of molecular weight 20,000 with isobutyl acrylate (BA), acrylic acid (AA), and 2-
Polymerization with (N-methylperfluorooctanesulfonamide) ethyl acrylate (MeFOSEA).

150部のメチルエチルケトン中の19部のPDMS、56部のB
A、15部のAAおよび10部のMeFOSEAの混合物に0.3部のア
ゾビス(イソブチロニトリル)および0.3部の四塩化臭
素を添加した。この溶液を窒素ガスでパージし、窒素雰
囲気下でビン中に密封した。ビンをLaunder-O-Meter
R中、55℃で54時間加熱し、大気圧で溶剤を蒸発させる
ことによってポリマーを回収した。
19 parts PDMS, 56 parts B in 150 parts methyl ethyl ketone
To a mixture of A, 15 parts AA and 10 parts MeFOSEA was added 0.3 parts azobis (isobutyronitrile) and 0.3 parts bromine tetrachloride. The solution was purged with nitrogen gas and sealed in a bottle under nitrogen atmosphere. Launder-O-Meter a bottle
The polymer was recovered by heating in R at 55 ° C. for 54 hours and evaporating the solvent at atmospheric pressure.

別個の実験において、150部のメチルエチルケトン中の2
2部のPDMS、54部のBA、14部のAAおよび10部のMeFOSEAの
混合物に、0.3部のアゾビス(イソブチロニトリル)を
添加した。この溶液を窒素ガスでパージし、窒素雰囲気
下でビン中に密封した。ビンをLaunder-O-MeterR中、55
℃で54時間加熱し、大気圧で溶剤を蒸発させることによ
ってポリマーを回収した。
In a separate experiment, 2 parts in 150 parts methyl ethyl ketone
To a mixture of 2 parts PDMS, 54 parts BA, 14 parts AA and 10 parts MeFOSEA was added 0.3 parts azobis (isobutyronitrile). The solution was purged with nitrogen gas and sealed in a bottle under nitrogen atmosphere. 55 in the Launder-O-Meter R
The polymer was recovered by heating at 0 ° C for 54 hours and evaporating the solvent at atmospheric pressure.

フロントページの続き (72)発明者 スマラジット ミトラ アメリカ合衆国 ミネソタ州 セント ポ ール,3エム センター(番地なし) (56)参考文献 特開 昭61−275365(JP,A) 特開 昭61−285425(JP,A)Front Page Continuation (72) Inventor Smalajit Mitra 3M Center (no address), St. Paul, Minnesota, USA (56) References JP 61-275365 (JP, A) JP 61-285425 (JP , A)

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】動物の毛髪または体に適用するための組成
物であって、 (a)液体分散媒中における溶液、分散体またはエマル
ションとしての (i)Aが存在する全てのモノマーの99重量%まで存在
し、1,1−ジヒドロパーフルオロアルカノールまたは1,1
−ジヒドロパーフルオロアルカノールの同族体、ω−ヒ
ドリドフルオロアルカノール、フルオロアルキルスルホ
ンアミドアルコール、環状フルオロアルキルアルコー
ル、およびフルオロエーテルアルコールの遊離基重合性
アクリル酸エステルまたはメタクリル酸エステルの少な
くとも1種であり; Bがコポリマー中における全モノマーの全重量の0.01〜
30重量%の量で存在し、Aと共重合性の少なくとも1種
の強化用モノマーであり;そして、 Cが存在する全モノマーの0.01〜50重量%の量で存在す
るモノマーであり、 一般式: X(Y)nSi(R)3-mZm (式中XはAおよびBモノマーと共重合性のビニル基で
あり; Yは二価結合基であり; Rは水素、低級アルキル、アリール、またはアルコキシ
であり; Zは少なくとも約500の数平均分子量を有し、かつ、共
重合条件下では本質的に非反応性である一価のシロキサ
ンポリマー部分であり; nは0または1であり; mは1−3の整数である)を有するモノマーである 反復A、BおよびCモノマーから成るコポリマー;およ
び (ii)10部のコポリマー当り0〜約500重量部の相溶性
溶剤または可塑剤から成る、組成物、および (b)医療用として有効量の薬物または化粧用として有
効量のコンディショナーもしくは化粧用として活性な成
分を含むことを特徴とする該組成物。
1. A composition for application to the hair or body of an animal, comprising: (a) a solution, dispersion or emulsion in a liquid dispersion medium (i) 99 weight of all monomers in which A is present. %, 1,1-dihydroperfluoroalkanol or 1,1
At least one of a homologue of a dihydroperfluoroalkanol, a ω-hydridofluoroalkanol, a fluoroalkylsulfonamide alcohol, a cyclic fluoroalkyl alcohol, and a fluoroether alcohol, a free radical polymerizable acrylic ester or methacrylic ester; B Is 0.01 to the total weight of all monomers in the copolymer
At least one reinforcing monomer present in an amount of 30% by weight and copolymerizable with A; and C being a monomer present in an amount of 0.01 to 50% by weight of the total monomers present; X (Y) n Si (R) 3-m Z m (wherein X is a vinyl group copolymerizable with A and B monomers; Y is a divalent linking group; R is hydrogen, lower alkyl, Aryl, or alkoxy; Z is a monovalent siloxane polymer moiety that has a number average molecular weight of at least about 500 and is essentially non-reactive under copolymerization conditions; n is 0 or 1 A; a copolymer having repeating A, B and C monomers; and (ii) 0 to about 500 parts by weight compatible solvent or plasticizer per 10 parts copolymer. And (b) a medically effective amount of Object or said composition comprising an active ingredient an effective amount of conditioner or cosmetically cosmetically.
【請求項2】動物の毛髪または体に適用するための組成
物であって、 該アクリル酸またはメタクリル酸エステルが、 CF3(CF2)xCH2OH, CF3(CF2)x(CH2)yOH, HCF2(CF2)x(CH2)yOH, (式中、xは0〜20であり、yは1〜10であり、zは0
〜7であり、qは2〜20であり、かつ、xより大きく、
rは1〜6であり、pおよびsは少なくとも1であり、
そして、R1は20炭素原子までのアルキルまたはアリール
(アルキル)または6環炭素原子までのシクロアルキル
である)から成る群内の式の弗素化化合物から選ばれる
請求項1記載の組成物。
2. A composition for application to the hair or body of an animal, wherein the acrylic acid or methacrylic acid ester is CF 3 (CF 2 ) x CH 2 OH, CF 3 (CF 2 ) x (CH 2 ) y OH, HCF 2 (CF 2 ) x (CH 2 ) y OH, (In the formula, x is 0 to 20, y is 1 to 10, and z is 0.
~ 7, q is 2-20, and greater than x,
r is 1 to 6, p and s are at least 1, and
And R 1 is selected from fluorinated compounds of the formula within the group consisting of alkyl or aryl (alkyl) up to 20 carbon atoms or cycloalkyl up to 6 ring carbon atoms.
【請求項3】動物の毛髪または体に適用するための組成
物であって、 該Cモノマーの該X基が一般式、 (式中、R7は水素またはCOOH基であり、そして、R8は水
素、メチル基またはCH2COOH基である)を有する請求項
2記載の組成物。
3. A composition for application to the hair or body of an animal, wherein the X group of the C monomer has the general formula: The composition of claim 2 having R 7 is hydrogen or a COOH group and R 8 is hydrogen, a methyl group or a CH 2 COOH group.
JP2207968A 1989-08-07 1990-08-06 Polysiloxane-graft copolymer composition Expired - Fee Related JPH0757737B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/390,227 US4972037A (en) 1989-08-07 1989-08-07 Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith
US390227 1989-08-07

Publications (2)

Publication Number Publication Date
JPH0376713A JPH0376713A (en) 1991-04-02
JPH0757737B2 true JPH0757737B2 (en) 1995-06-21

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Country Link
US (1) US4972037A (en)
EP (1) EP0412771B1 (en)
JP (1) JPH0757737B2 (en)
AU (2) AU5989490A (en)
CA (1) CA2021580C (en)
DE (1) DE69022801T2 (en)

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US5021477A (en) * 1989-08-07 1991-06-04 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer topical binder composition with novel hydrophilic monomers and method of coating therewith
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US5209924A (en) * 1989-08-07 1993-05-11 Minnesota Mining And Manufacturing Company Polysiloxane-grafted copolymer topical binder composition with novel fluorochemical comonomer and method of coating therewith
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AU5989490A (en) 1991-02-07
EP0412771A1 (en) 1991-02-13
JPH0376713A (en) 1991-04-02
DE69022801D1 (en) 1995-11-09
AU651038B2 (en) 1994-07-07
EP0412771B1 (en) 1995-10-04
CA2021580A1 (en) 1991-02-08
US4972037A (en) 1990-11-20
CA2021580C (en) 2002-12-03
DE69022801T2 (en) 1996-05-15
AU5210793A (en) 1994-02-17

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